Tetraazaannulene cobalt complex compounds and method for preparation therefor

ABSTRACT

A tetraazaannulene cobalt complex compound having the general formula (I); ##STR1## wherein R 1 , R 2  and R 3  each independently is a hydrogen atom, a C 1-8  alkoxy group or a C 1-8  alkyl group but in case of one of R 1 , R 2  and R 3  being a hydrogen atom the other two groups are not hydrogen atoms at the same time, and when R 1  is a methyl group R 2  and R 3  are not hydrogen atoms at the same time.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a tetraazaannulene cobalt complex compound (hereinafter referred to Co-TAA) useful as an oxygen reduction catalyst and a method for the preparation of the Co-TAA.

2. Description of the Prior Art

Various kinds of oxygen reduction catalysts have been known. Especially, platinum has been well known as an oxygen reduction catalyst because of the superior catalytic properties. However, it is difficult to practically employ platinium as a catalyst in a fuel battery because platinum is expensive and a rare metal. Therefore, the development of new catalysts having a low oxygen reduction voltage and a high catalytic activity have been desired and made. However, the catalysts which can take the place of platinum have not been found.

The Co-TAA having the formula (VII); ##STR2## is reported as an oxygen reduction catalyst having a high activity in F. Beck et al, Z. Naturforsch. 28a, 1009-1021(1973), and DE-OS No. 20 46 354. However, the catalyst life of the Co-TAA of the formula (VII) is short and, in addition, the catalyst activity is not satisfactory.

Further, the Co-TAA having the formula (VIII); ##STR3## is reported in Y. Nishida et al, Bulletin of the Chemical Society of Japan, Vol. 50(9), 2485-2486 (1977). There is no description relating to the oxygen reduction catalyst properties of the Co-TAA of the formula (VIII) in the report. The inventors of this invention have produced the Co-TAA of the formula (VIII) to measure the catalytic properties, and found that the catalyst activity is insufficient though the catalyst life is long.

A method for the preparation of the Co-TAA is described in Y. Nishida et al, Journal of Coordination Chemistry, Vol. 9, 161-166 (1979). This method, however, has a defect that the reaction procedures and the aftertreatments are difficult due to the use of sulfur and acetyl hydroperoxide in the production of the starting material, that is, dithiolium hydrogensulfate. Further, this method has such defects that the yields of the tetraazaannulene and the Co-TAA are low, that the purity of the Co-TAA is also low and that the purification of the Co-TAA is difficult.

SUMMARY OF THE INVENTION

An object of this invention is to provide a novel Co-TAA.

Another object of this invention is to provide a novel method for preparing the Co-TAA including conventional Co-TAA, and a tetraazaannulene derivative which is an intermediate of the Co-TAA.

Accordingly, this invention provides a novel Co-TAA having the general formula (I); ##STR4## wherein R₁, R₂ and R₃ each independently is a hydrogen atom, a C₁₋₈ alkoxy group or a C₁₋₈ alkyl group but in case of one of R₁, R₂ and R₃ being a hydrogen atom the other two groups are not hydrogen atoms at the same time, and when R₁ is a methyl group R₂ and R₃ are not hydrogen atoms at the same time.

DETAILED DESCRIPTION OF THE INVENTION

Suitable examples Co-TAA of this invention of the formula (I) include;

(1) R₁ is a C₁₋₈ alkoxy group,

(2) R₁ and R₂ each independently is a C₁₋₈ alkoxy group,

(3) R₁ and R₂ each independently is a C₁₋₈ alkoxy group and R₃ is a hydrogen atom,

(4) each of R₁, R₂ and R₃ independently is a C₁₋₈ alkoxy group,

(5) R₁ is a C₁₋₈ alkoxy group and R₂ and R₃ are the same and C₁₋₈ alkoxy groups,

(6) R₁ is a C₁₋₈ alkoxy group and R₂ and R₃ are both hydrogen atoms,

(7) R₁ is a C₁₋₈ alkoxy group and R₂ and R₃ each independently is a C₁₋₈ alkyl group,

(8) R₁ is a C₁₋₈ alkoxy group and R₂ and R₃ are the same and C₁₋₈ alkyl groups,

(9) R₁ is a C₁₋₈ alkyl group,

(10) R₁ is a C₁₋₈ alkyl group and R₂ and R₃ each independently is a C₁₋₈ alkoxy group,

(11) R₁ is a C₁₋₈ alkyl group and R₂ and R₃ are the same and C₁₋₈ alkoxy groups,

(12) each of R₁, R₂ and R₃ independently is a C₁₋₈ alkyl group,

(13) R₁ is a C₁₋₈ alkyl group and R₂ and R₃ are the same and C₁₋₈ alkyl groups,

(14) R₁ is a C₂₋₈ alkyl group and R₂ and R₃ are both hydrogen atoms,

(15) R₁ is a hydrogen atom,

(16) R₁ is a hydrogen atom and R₂ is a C₁₋₈ alkoxy group,

(17) R₁ is a hydrogen atom and R₂ and R₃ each independently is a C₁₋₈ alkoxy group,

(18) R₁ is a hydrogen atom and R₂ and R₃ are the same and C₁₋₈ alkoxy groups,

(19) R₁ and R₃ are both hydrogen atoms and R₂ is a C₁₋₈ alkoxy group,

(20) R₁ is a hydrogen atom and R₂ is a C₁₋₈ alkyl group,

(21) R₁ is a hydrogen atom and R₂ and R₃ each independently is a C₁₋₈ alkyl group,

(22) R₁ is a hydrogen atom and R₂ and R₃ are the same and C₁₋₈ alkyl groups, and

(23) R₁ and R₃ are both hydrogen atoms and R₂ is a C₁₋₈ alkyl group.

Preferred R₁, R₂ and R₃ include a hydrogen atom, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an iso-butoxy group, a n-pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group and a n-octyl group.

Preferred Co-TAA of this invention is the compound of the formula (I) where one or two of R₁, R₂ and R₃ are methoxy groups, for example, one or two of R₁, R₂ and R₃ are methoxy groups and the other group or groups are hydrogen atoms, R₁ is a methoxy group and R₂ and R₃ are the same and C₄₋₈ alkoxy groups, R₁ is a methoxy group and R₂ and R₃ are the same and C₁₋₄ alkyl groups, R₁ is a C₄₋₈ alkoxy group and R₂ and R₃ are both methoxy groups, R₁ is a C₁₋₄ alkyl group and R₂ and R₃ are both methoxy groups, and all of R₁, R₂ and R₃ are methoxy groups; the compound of the formula (I) where one or two of R₁, R₂ and R₃ are methyl groups and the other group or groups are C₁₋₄ alkyl groups or C₄₋₈ alkoxy groups, for example, R₁ is a methyl group and R₂ and R₃ are the same and C₁₋₄ alkyl groups or C₄₋₈ alkoxy group, and R₂ and R₃ are both methyl groups and R₁ is a C₁₋₄ alkyl group or a C₄₋₈ alkoxy group; the compound of the formula (I) where R₁, R₂ and R₃ are all methyl groups; the compound of the formula (I) where R₁ and R₂ are the same and C₄₋₈ alkoxy groups and R₃ is a hydrogen atom; the compound of the formula (I) where R₁ is a C₁₋₄ alkoxy group and R₂ and R₃ are the same and C₁₋₄ alkyl groups; or the compound of the formula (I) where R₁, R₂ and R₃ are all n-butoxy groups.

More specifically, preferred examples of the Co-TAA having a higher catalyst activity and a longer catalyst life include ##STR5##

The Co-TAA including the novel Co-TAA of this invention, which can be represented by the general formula (II); ##STR6## wherein R₄ is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ acyloxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ acylamino group, a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group, a N,N-di C₁₋₆ alkylamino C₁₋₃ alkyl group, or an amino group;

n is integer of 1 to 5; and

R₅ and R₆ each independently is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ acyloxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group, or a C₁₋₈ acylamino group;

can be obtained by the following four methods. ##STR7##

In the above described formulae (III), (IV), (V) and (VI), R₄, R₅, R₆ and n are the same as defined in the formula (II); R₇ is a C₁₋₆ alkyl group; and R₈ and R₉ each independently is a C₁₋₆ alkyl group.

According to Method 1, the Co-TAA of the formula (II) can be obtained by reacting a β-alkoxy-α-arylacrolein of the general formula (III) with an o-phenylenediamine derivative of the general formula (IV) to prepare a tetraazaannulene derivative of the formula (V), and then reacting the tetraazaannulene derivative (V) with a cobalt compound.

The reaction (A) between the β-alkoxy-α-arylacrolein (III) and the o-phenylenediamine derivative (IV) can be carried out at 50° C.-250° C. either in the absence of a solvent or in the presence of a solvent. Preferably, the reaction (A) is carried out in the presence of a solvent at around the boiling point of the solvent employed.

Preferred n in the formula (III) of the β-alkoxy-α-arylacroleins which can be employed in the reaction (A) is one.

Preferred R₄ in the formula (III) of the β-alkoxy-α-arylacroleins which can be employed in the reaction (A) is in the para position.

Exemplary β-alkoxy-α-arylacroleins (III) which can be employed in the reaction (A) include β-ethoxy-α-phenylacrolein, β-ethoxy-α-(p-nitrophenyl)acrolein, β-ethoxy-α-(p-methoxyphenyl)acrolein, β-ethoxy-α-(p-tolyl)acrolein, β-ethoxy-α-[p-(n-butyl)phenyl]acrolein, β-ethoxy-α-(p-cyanophenyl)acrolein, β-ethoxy-α-(p-chlorophenyl)acrolein, β-ethoxy-α-(p-bromophenyl)acrolein, β-ethoxy-α-[p-(ethoxycarbonyl)phenyl]acrolein, β-ethoxy-α-(p-carboxyphenyl)acrolein, β-ethoxy-α-(p-carbamoylphenyl)acrolein, β-ethoxy-α-(p-hydroxyphenyl)acrolein, β-ethoxy-α-[p-(N,N-dimethylaminomethyl)phenyl]acrolein, β-ethoxy-α-[p-(N,N-dimethylamino)phenyl]acrolein, β-ethoxy-α-[p-(ethoxycarbonylmethyl)phenyl]acrolein and the similar acroleins as described above, whose β-position of the acroleins is a methoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a n-pentyloxy group, a hexyloxy group or a cycrohexyloxy group.

Preferred R₄ in the formula (III) of the β-alkoxy-α-arylacroleins which can be employed in the reaction (A) is a hydrogen atom, a methoxy group, a methyl group, a halogen atom, a nitro group, a cyano group or a carboxyl group. Accordingly, preferred β-alkoxy-α-arylacroleins (III) include β-ethoxy-α-phenylacrolein, β-ethoxy-α-(p-nitrophenyl)acrolein, β-ethoxy-α-(p-methoxyphenyl)acrolein, β-ethoxy-α-(p-tolyl)acrolein, β-ethoxy-α-(p-cyanophenyl)acrolein, β-ethoxy-α-(p-chlorophenyl)acrolein, β-ethoxy-α-(p-bromophenyl)acrolein and β-ethoxy-α-(p-carboxyphenyl)acrolein.

The β-alkoxy-α-arylacroleins of the general formula (III) can be obtained by hydrolyzing the β-N,N-dialkylamino-α-arylacrolein of the general formula (VI) and reacting the compound obtained with a C₁₋₆ alkyl halide. The methods for preparing the β-alkoxy-α-arylacroleins (III) are easier than those for preparing dithiolium hydrogensulfate which is the starting material of known methods. Therefore, there is a good possibility that the method of this invention will be able to provide various kinds of the Co-TAA.

Exemplary o-phenylenediamine derivatives (IV) which can be employed in the reaction (A) include o-phenylenediamine, 4-(C₁₋₈ alkoxy)-o-phenylenediamines, 4-(C₁₋₈ alkyl)-o-phenylenediamines, 4,5-di C₁₋₈ alkyl-o-phenylenediamine, 4,5-dichloro-o-phenylenediamine, 4-nitro-o-phenylenediamine, 4-chloro-o-phenylenediamine, 4-carbamoyl-o-phenylenediamine, 4-carboxy-o-phenylenediamine, 4-cyano-o-phenylenediamine, 4-dimethylamino-o-phenylenediamine, 4,5-di C₁₋₈ alkoxy-o-phenylenediamine, 4-ethoxycarbonylmethyl-o-phenylenediamine, 4-carboxy-5-methyl-o-phenylenediamine and 4-ethoxycarbonyl-o-phenylenediamine.

Preferred R₅ and R₆ in the o-phenylenediamine derivatives (IV) which can be employed in the reaction (A) include a hydrogen atom, a methoxy group, a methyl group, a halogen atom, a nitro group and a carboxyl group. Accordingly, preferred o-phenylenediamine derivatives (IV) include o-phenylenediamine, 4-methyl-o-phenylenediamine, 4-chloro-o-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, 4,5-dichloro-o-phenylenediamine, 4-nitro-o-phenylenediamine, 4-methoxy-o-phenylenediamine and 4-carboxy-5-methyl-o-phenylenediamine.

The solvents which can be employed in the reaction (A) include alcohols, phenols, cyclic ethers and non-proton polar organic solvents such as N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorictriamide and N-methylpyrrolidone. The reaction (A) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the desired compounds of the formula (V) can be obtained as pure crystals in a higher yield when the reaction solution is cooled.

The reaction (B) between the tetraazaannulene derivative of the formula (V) as obtained in the reaction (A) and a cobalt compound can be carried out in the presence of a solvent at 50° C.-250° C. Preferably, the reaction (B) is carried out at around the boiling point of the solvent employed.

Exemplary cobalt compounds which can be employed in the reaction (B) include cobalt salts of organic acids such as cobalt (II) carbonate, cobalt (II) acetate, cobalt (II) lactate, cobalt (II) oxalate, cobalt (II) citrate, cobalt (II) tartarate and cobalt (II) gluconate; cobalt salts of inorganic acids such as cobalt (II) chloride, cobalt (II) bromide and cobalt (II) iodide; and cobalt complex salts such as cobalt (II) acetylacetonato.

The solvents which can be employed in the reaction (B) include alcohols, phenols, cyclic ethers and non-proton polar organic solvents such as N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorictriamide and N-methylpyrrolidone. The reaction (B) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield.

According to Method 2, the Co-TAA of the formula (II) can be obtained by reacting a β-alkoxy-α-arylacrolein of the general formula (III) with an o-phenylenediamine derivative of the general formula (IV) in the presence of a cobalt compound.

The reaction (C) among the β-alkoxy-α-arylacrolein (III), the o-phenylenediamine derivative (IV) and the cobalt compound can be carried out at 50° C.-250° C. either in the absence of a solvent or in the presence of a solvent. Preferably, the reaction (C) is carried out in the presence of a solvent at around the boiling point of the solvent employed.

The mol ratio of the β-alkoxy-α-arylacrolein (III): the o-phenylenediamine derivative (IV): the cobalt compound which can be employed in the reaction (C) is 2:2:1.

Preferred n in the β-alkoxy-α-arylacroleins of the formula (III) which can be employed in the reaction (C) is one.

Preferred R₄ in the β-alkoxy-α-arylacroleins of the formula (III) which can be employed in the reaction (C) is in the para position.

Exemplary β-alkoxy-α-arylacroleins (III) which can be employed in the reaction (C) include the same acroleins as those employed in the reaction (A) of Method 1.

Preferred R₄ in the β-alkoxy-α-arylacroleins of the formula (III) which can be employed in the reaction (C) includes a hydrogen atom, a methoxy group, a methyl group, a halogen atom, a nitro group and a cyano group. Accordingly, preferred β-alkoxy-α-arylacroleins (III) which can be employed in the reaction (C) include β-ethoxy-α-phenylacrolein, β-ethoxy-α-(p-nitrophenyl)acrolein, β-ethoxy-α-(p-methoxyphenyl)acrolein, β-ethoxy-α-(p-tolyl)acrolein, β-ethoxy-α-(p-cyanophenyl)acrolein, β-ethoxy-α-(p-chlorophenyl)acrolein and β-ethoxy-α-(p-bromophenyl)acrolein.

Exemplary o-phenylenediamine derivatives (IV) which can be employed in the reaction (C) include the same o-phenylenediamines as those employed in the reaction (A) of Method 1.

Preferred R₅ and R₆ in the o-phenylenediamine derivative (IV) which can be employed in the reaction (C) include a hydrogen atom, a methoxy group, a methyl group and a halogen atom. Accordingly, preferred o-phenylenediamine derivatives (IV) include o-phenylenediamine, 4-methyl-o-phenylenediamine, 4-chloro-o-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, 4,5-dichloro-o-phenylenediamine and 4-methoxy-o-phenylenediamine.

Exemplary cobalt compounds and the solvents which can be employed in the reaction (C) include the same as those employed in the reaction (B) of Method 1.

The reaction (C) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield. Further, the yield of the products obtained in Method 2 is higher than that of Method 1.

According to Method 3, the Co-TAA of the formula (II) can be obtained by reacting a β-N,N-dialkylamino-α-arylacrolein of the general formula (VI) with an o-phenylenediamine derivative of the general formula (IV) to prepare a tetraazaannulene derivative of the formula (V), and reacting the tetraazaannulene derivative with a cobalt compound.

The reaction (D) between the β-N,N-dialkylamino-α-arylacrolein (VI) and the o-phenylenediamine derivative (IV) can be carried out at 50° C.-250° C. either in the absence of or in the presence of a solvent. Preferably, the reaction (D) is carried out in the presence of a solvent at around the boiling point of the solvent employed.

Preferred n in the β-N,N-dialkylamino-α-arylacrolein of the formula (VI) which can be employed in the reaction (D) is one.

Preferred R₄ in the β-N,N-dialkylamino-α-arylacrolein of the formula (VI) which can be employed in the reaction (D) is in the para position.

Exemplary β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (D) include β-dimethylamino-α-phenylacrolein, β-dimethylamino-α-[p-(C₁₋₈ alkoxy)phenyl]acroleins, β-dimethylamino-α-[p-(C₁₋₈ alkyl)phenyl]acroleins, β-dimethylamino-α-(p-nitrophenyl)acrolein, β-dimethylamino-α-[p-(dimethylamino)phenyl]acrolein, β-dimethylamino-α-(p-cyanophenyl)acrolein, β-dimethylamino-α-(p-chlorophenyl)acrolein, β-dimethylamino-α-[p-(ethoxycarbonylmethyl)phenyl]acrolein, β-dimethylamino-α-(p-carboxyphenyl)acrolein, β-dimethylamino-α-(p-carbamoylphenyl)acrolein, β-dimethylamino-α-(p-hydroxyphenyl)acrolein, β-dimethylamino-α-[p-(ethoxycarbonyl)phenyl]acrolein and the similar acroleins as described above, whose β-position of the acroleins is a diethylamino group, a dipropylamino group, a dibutylamino group, a (N-methyl,N-ethyl)amino group or a (N-methyl,N-butyl)amino group.

Preferred R₄ in the β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (D) is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a nitro group or an ethoxycarbonyl group.

Preferred R₈ and R₉ in the β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (D) include a methyl group, an ethyl group, a n-propyl group and a n-butyl group.

The β-N,N-dialkylamino-α-arylacroleins of the general formula (VI) can be produced by referring to the methods described in Z. Arnold, Collection of Czechoslov. Chem. Commun. Vol. 26, 3051(1961).

Exemplary o-phenylenediamine derivatives (IV) which can be employed in the reaction (D) include the same o-phenylenediamines as those employed in the reaction (A) of Method 1.

Preferred R₅ and R₆ in the o-phenylenediamine derivatives (IV) which can be employed in the reaction (D) include a hydrogen atom, a C₁₋₈ alkoxy group, a halogen atom and a C₁₋₈ alkyl group.

The solvents which can be employed in the reaction (D) include the same solvents as those employed in the reaction (A) of Method 1. The reaction (D) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the compounds of the formula (V) can be obtained in the pure form in a higher yield.

The reaction (E) between the tetraazaannulene derivative of the formula (V) as obtained in the reaction (D) and a cobalt compound can be carried out in the presence of a solvent at 50° C.-250° C. Preferably, the reaction (E) is carried out at around the boiling point of the solvent employed.

The cobalt compounds and the solvents which can be employed in the reaction (E) include the same as those employed in the reaction (B) of Method 1.

The reaction (E) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield.

According to Method 4, the Co-TAA of the formula (II) can be obtained by reacting a β-N,N-dialkylamino-α-arylacrolein of the general formula (VI) with an o-phenylenediamine derivative of the formula (IV) in the presence of a cabalt compound.

The reaction (F) among the β-N,N-dialkylamino-α-arylacrolein (VI), the o-phenylenediamine derivative (IV) and the cobalt compound can be carried out at 50° C.-250° C. either in the absence of or in the presence of a solvent. Preferably, the reaction (F) is carried out in the presence of a solvent at around the boiling point of the solvent employed.

The mol ratio of the β-N,N-dialkylamino-α-arylacrolein (VI): the o-phenylenediamine derivative (IV): the cobalt compound which can be employed in the reaction (F) is 2:2:1.

Preferred n in the β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (F) is one.

Preferred R₄ in the β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (F) is in the para position.

Exemplary β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (F) include the same acroleins as those employed in the reaction (D) of Method 3.

Preferred R₄ in the β-N,N-dialkylamino-α-arylacroleins of the formula (VI) which can be employed in the reaction (F) is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group or an ethoxycarbonyl group.

Preferred R₈ and R₉ in the β-N,N-dialkylamino-α-arylacroleins (VI) which can be employed in the reaction (F) include a methyl group, an ethyl group, a n-propyl group and a n-butyl group.

Exemplary o-phenylenediamine derivative (IV) which can be employed in the reaction (F) include the same o-phenylenediamines as those employed in the reaction (D) of Method 3.

Preferred R₅ and R₆ in the o-phenylenediamine derivatives (IV) which can be employed in the reaction (F) include a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group and a halogen atom.

Exemplary cobalt compounds and the solvents which can be employed in the reaction (F) include the same as those employed in the reaction (E) of Method 3.

The reaction (F) can be preferably carried out in the presence of the non-proton polar organic solvent at around the boiling point of the solvent employed because the products of the formula (II) can be obtained in the pure form in a higher yield. Further, the yield of the products obtained in Method 4 is higher than that of Method 3.

The novel compound (I) of this invention can be prepared by reacting the β-C₁₋₈ alkoxy-α-(p-hydroxyphenyl)acrolein with an o-phenylenediamine derivative (IV) where R₅ and R₆ each independently is a hydrogen atom, a C₁₋₈ alkoxy group or a C₁₋₈ alkyl group in the presence of a cobalt compound, and reacting the compound obtained with a C₁₋₈ alkyl halide. (Method 5) The reaction (G) among the β-C₁₋₈ alkoxy-α-(p-hydroxyphenyl)acrolein, the o-phenylenediamine derivative (IV) and the cobalt compound can be carried out under the same reaction conditions as those of the reaction (F). The reaction between the compound as obtained in the reaction (G) and the C₁₋₈ alkyl halide can be carried out in the presence of a solvent for the compound at 25° C.-100° C.

In each of Method 1-5, the products are confirmed as the Co-TAA of the formula (I) or the formula (II), or the tetraazaannulene derivatives of the formula (V) by the value of physical properties such as elementary analysis, Mass spectra and visible spectra of the products obtained.

The Co-TAA of the formulae (I) and (II) are useful as an oxygen reduction catalyst and the tetraazaannulene derivatives of the formula (V) are useful as the intermediate of the Co-TAA.

The following examples illustrate the present invention in more detail, but they are given for illustrative purposes only and are not to be construed as limiting the invention. EXAMPLE 1 ##STR8##

In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (540 mg) of o-phenylenediamine and 2.5 millimol (623 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 120° C. for 30 minutes. The solution was added with 5 millimol (1025 mg) of β-dimethylamino-α-(p-methoxyphenyl)acrolein and refluxed under heating for 3 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give dark purple crystals in a yield of 60.0%.

The crystals have the following physical values.

Mass Spectrum: Calcd: 557.5. Found: 557.

Elementary Analysis: Calcd.: C:H:N=68.94:4.70:10.05. Found: C:H:N=68.83:4.76:10.25.

Visible Spectrum (nm) [in DMF]: 380(s)*, 397, 429(s) and 522

EXAMPLE 2 ##STR9##

In 10 ml of N,N-dimethylformamide were dissolved 2.5 millimol (270 mg) of o-phenylenediamine and 1.25 millimol (312 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 120° C. for 30 minutes. Then, the solution was added with 2.5 millimol (612.5 mg) of β-dimethylamino-α-(p-n-butoxyphenyl)acrolein and refluxed under heating for 3 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give dark purple crystals in a yield of 45.4%.

The crystals have the following physical values.

Mass Spectrum: Calcd.: 641.7. Found: 641.

Elementary Analysis: Calcd.: C:H:N=71.13:5.97:8.73. Found: C:H:N=70.95:6.01:8.77.

Visible Spectrum (nm) [in DMF]: 380(s)*, 397, 429(s) and 522.

EXAMPLE 3 ##STR10##

In 10 ml of N,N-dimethylformamide were dissolved 2.5 millimol (420 mg) of 4,5-dimethoxy-o-phenylenediamine, 1.25 millimol (312 mg) of cobalt (II) acetate tetrahydrate and 2.5 millimol (513 mg) of β-dimethylamino-α-(p-methoxyphenyl)acrolein, and the solution was refluxed under heating in an argon gas atmosphere for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give dark purple crystals in a yield of 17.0%.

The crystals have the following physical values.

Mass Spectrum: Calcd.: 667.6. Found: 667.

Elementary Analysis: Calcd.: C:H:N=63.81:5.06:8.27. Found: C:H:N=63.77:4.88:8.40.

Visible Spectrum (nm) [in DMF]: 384, 395(s)*, 430, 457 and 525.

EXAMPLE 4 ##STR11##

In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (690 mg) of 4-methoxy-o-phenylenediamine and 2.5 millimol (625 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 120° C. for 30 minutes. Then, the solution was added with 5 millimol (955 mg) of β-dimethylamino-α-(p-hydroxyphenyl)acrolein, and refluxed under heating in an argon gas atmosphere for 5 hours. The reaction solution was cooled and added with methanol to precipitated crystals. The crystals were separated by filtration, washed with methanol and dried. The yield was 7.5%. ##STR12##

In 10 ml of N,N-dimethylformamide was dissolved the crystals obtained in Step 1. To the solution obtained were added 6 times amount of propyl iodide based on the millimol of the crystals and 6 times amount of potassium carbonate based on the millimol of the crystals. Then, the mixture was stirred at 25° C. for 12 hours. To the reaction mixture was added excess of water to precipitated crystals. The crystals were obtained by filtration, washed with methanol and dried to give dark purple crystals in a yield of 50%.

The crystals have the following physical values.

Mass Spectrum: Calcd.: 673.7. Found: 673.

Elementary Analysis: Calcd.: C:H:N=67.75:5.69:8.32. Found: C:H:N=68.01:5.55:8.25.

Visible Spectrum (nm) [in DMF]: 399, 420(s)*, 443(s), 388(s) and 520

EXAMPLE 5 ##STR13##

In 10 ml of N,N-dimethylformamide were dissolved 2.5 millimol (473 mg) of β-dimethylamino-α-(p-methylphenyl)acrolein, 1.25 millimol (312 mg) of cobalt (II) acetate tetrahydrate and 2.5 millimol (340 mg) of 4,5-dimethyl-o-phenylenediamine, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give brown crystals in a yield of 68.8%.

The crystals have the following physical values.

Mass Spectrum: Calcd.: 581.6. Found: 581.

Elementary Analysis: Calcd.: C:H:N=74.34:5.89:9.63. Found: C:H:N=74.43:5.87:9.61.

Visible Spectrum (nm) [in DMF]: 384, 398, 423, 440(s)* and 524

EXAMPLES 6˜209

Co-TAA of this invention was prepared by the methods as shown in Table 1. The results are also shown in Table 1.

    TABLE 1-1              Example       ##STR14##       ##STR15##       of ReactionExample No. Yield Crystal       ##STR16##       No. R.sub.1 R.sub.2 R.sub.3 Conditions (%) Color R.sub.1 R.sub.2      R.sub.3  6 OC.sub.2 H.sub.5 H H 2 43.6 Dark Purple OC.sub.2 H.sub.5 H H      7 OCH.sub.2 CH.sub.2 CH.sub.3 H H 2 42.2 " OCH.sub.2 CH.sub.2 CH.sub.3 H H       8 H OCH.sub.3 H 1 8.9 " H OCH.sub.3 H 9 H OC.sub.2 H.sub.5 H 3 7.7 " H      OC.sub.2       H.sub.5 H 10 OCH(CH.sub.3).sub.2 H H 2 40.7 " OCH(CH.sub.3).sub.2 H H      11       ##STR17##       H H 2 44.1 "       ##STR18##       H H  12 OCH.sub.2 CH(CH.sub.3).sub.2 H H 2 46.3 " OCH.sub.2       CH(CH.sub.3).sub.2 H H 13 H OCH.sub.3 OCH.sub.3 3 0.52 Reddish Purple H O      CH.sub.3 OCH.sub.3 14 H  OCH.sub.2 CH.sub.2 CH.sub.3 H 3 6.2 Dark Purple H       OCH.sub.2 CH.sub.2 CH.sub.3 H 15 H OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      H 3 9.8 " H OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 H 16 H OC.sub.2 H.sub.5      OC.sub.2 H.sub.5 3 0.95 Reddish Purple H OC.sub.2 H.sub.5 OC.sub.2      H.sub.5 17 H OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 3      1.4 " H OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 18 H      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      3 1.0 Dark Purple H OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.2 CH.sub.3 19 OCH.sub.3 OCH.sub.3 H 1 15.0 Reddish Purple O      CH.sub.3 OCH.sub.3 H 20 OCH.sub.3 OC.sub.2 H.sub.5 H 3 13.2 "  OCH.sub.3 O      C.sub.2 H.sub.5 H 21 OCH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 H 3 12.6 "      OCH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 H 22 OCH.sub.3 OCH(CH.sub.3).sub.2 H       3 11.5 Reddish Purple OCH.sub.3 OCH(CH.sub.3).sub.2 H 23 OCH.sub.3      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 H 3 18.8 " OCH.sub.3 OCH.sub.2      (CH.sub.2).sub.2 CH.sub.3 H       24 OCH.sub.3      ##STR19##       H 3 15.3 " OCH.sub.3       ##STR20##       H  25 OCH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 H 3 17.7 " OCH.sub.3      OCH.sub.2 CH(CH.sub.3).sub.2 H 26 OCH.sub.3 OC(CH.sub.3).sub.3 H 3 10.6      " OCH.sub.3 OC(CH.sub.3).sub.3 H 27 OCH.sub.3 OC.sub.2 H.sub.5 OC.sub.2      H.sub.5 3 3.0 Dark Purple OCH.sub.3 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 28 O      CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 3 14.4      " OCH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 29      OCH.sub.3 OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2 3 9.6 " OCH.sub.3      OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2 30 OCH.sub.3 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 3 7.5      Dark Brown OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.2 CH.sub.3       31 OCH.sub.3      ##STR21##       ##STR22##       3 6.3 " OCH.sub.3       ##STR23##       ##STR24##        32 OCH.sub.3 OCH.sub.2 CH(CH.sub. 3).sub.2OCH.sub.2 CH(CH.sub.3).sub.2      3 7.9 " OCH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2       CH(CH.sub.3).sub.2 33 OC.sub.2 H.sub.5 OCH.sub.3 H 3 6.6 Reddish Purple O      C.sub.2 H.sub.5 OCH.sub.3 H 34 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 H 3      14.2 " OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 H 35 OC.sub.2 H.sub.5 OCH.sub.2      CH.sub.2 CH.sub.3 H 3 5.9 " OC.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 CH.sub.3 H       36 OC.sub.2 H.sub.5 OCH(CH.sub.3).sub.2 H 3 4.8 " OC.sub.2 H.sub.5      OCH(CH.sub.3).sub.2 H 37 OC.sub.2 H.sub.5 OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 H 3 7.3 Dark Purple OC.sub.2 H.sub.5 OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 H 38 OC.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 3 15.2 Dark Purple      OC.sub.2 H.sub.5  OCH.sub.3 OCH.sub.3 39 OC.sub.2 H.sub.5 OC.sub.2      H.sub.5 OC.sub.2 H.sub.5 3 10.5 " OC.sub.2 H.sub.5 OC.sub.2 H.sub.5      OC.sub.2 H.sub.5 40 OC.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 CH.sub.3      OCH.sub.2 CH.sub.2 CH.sub.3 3 7.5 Dark Brown OC.sub.2 H.sub.5 OCH.sub.2      CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 41 OC.sub.2 H.sub.5      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      3 4.8 " OC.sub.2 H.sub.5 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.2 CH.sub.3 42 OCH.sub.2 CH.sub.2 CH.sub.3 OC.sub.2      H.sub.5 H 3 5.2 Reddish Purple OCH.sub.2 CH.sub.2 CH.sub.3 OC.sub.2      H.sub.5 H 43 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 H 3      16.8 " OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 H 44      OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 H 3 6.5      Dark Purple OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 H 45 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 3 9.8 "      OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 46 OCH.sub.2 CH.sub.2      CH.sub.3 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 3 2.3 Dark Purple OCH.sub.2      CH.sub.2 CH.sub.3 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 47 OCH.sub.2      CH.sub.2 CH.sub.3 OCH.sub. 2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2      CH.sub.3 3 8.1 Dark Brown OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2      CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 48 OCH.sub.2 CH.sub.2 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      3 3.2 " OCH.sub.2 CH.sub. 2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 O      CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 49 OCH(CH.sub.3).sub.2 OCH.sub.3 H 3      7.8 Reddish Purple OCH(CH.sub.3).sub.2 OCH.sub.3 H 50 OCH(CH.sub.3).sub.2       OCH(CH.sub.3).sub.2 H 3 6.2 " OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2 H      51 OCH(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 3 8.7 Dark Purple OCH(CH.sub.3      ).sub.2 OCH.sub.3 OCH.sub.3 52 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      OCH.sub.3 H 3 47.0 Reddish Purple OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      OCH.sub.3 H 53 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OC.sub.2 H.sub.5 H 3      10.1 Dark Brown OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OC.sub.2 H.sub.5 H      54 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 H 3      11.0 Dark Brown OCH.sub.2 (CH.sub.2).sub. 2 CH.sub.3 OCH.sub.2 CH.sub.2      CH.sub.3 H 55 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 H 3 13.3 " OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 H 56 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 3 5.3 " OCH.sub.2      (CH.sub.2).sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 57 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 3 1.9 "      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 58 O      CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2      CH.sub.2 CH.sub.3 3 4.7 " OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2      CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 59 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.  2).sub.2 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 3 6.9 " OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3       60      ##STR25##       OCH.sub.3 H 3 37.8 Reddish Purple       ##STR26##       OCH.sub.3 H       61      ##STR27##       ##STR28##       H 3 8.1 Dark Purple       ##STR29##       ##STR30##       H       62      ##STR31##       OCH.sub.3 OCH.sub.3 3 7.2 Dark Brown       ##STR32##       OCH.sub.3 OCH.sub.3  63 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.3 H 3 42.7      Reddish Purple OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.3 H 64 OCH.sub.2      CH(CH.sub.3).sub.2 OCH.sub.2 CH(CH.sub.3).sub.2 H 3 12.4 Dark Purple      OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 CH(CH.sub.3).sub.2 H 65 OCH.sub.2      CH(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 3 10.3 Dark Brown OCH.sub.2      CH(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 66 OC(CH.sub.3).sub.3 H H 2 33.2      Dark Purple OC(CH.sub.3).sub.3 H H 67 OC(CH.sub.3).sub.3 OCH.sub.3 H 3      27.3 " OC(CH.sub.3).sub.3 OCH.sub.3 H 68 OC(CH.sub.3).sub.3 OCH.sub.3      OCH.sub.3 3 5.9 Dark Brown OC(CH.sub.3).sub.3 OCH.sub.3 OCH.sub.3 69      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H H 3 46.2 Dark Purple OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 H H 70 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 H H      3 38.9 Dark Purple OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3 H H 71 H OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H 3 10.3 " H      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H 72 H OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 H 3 6.5 " H OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 H 73 OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 OCH.sub.3 H 3 28.1 Brown OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH.sub.3 H 74 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 OCH.sub.3 H 3 23.6 Dark Brown OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 OCH.sub. 3 H 75 OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H      3 31.8 Reddish Brown OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H 76      OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 H 3 25.5 Brown OCH.sub.3      OCH.sub.2 (CH.sub. 2).sub.6 CH.sub.3 H 77 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 OCH(CH.sub.3).sub.2 H 3 13.7 Dark Brown OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH(CH.sub.3).sub.2 H 78 OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 OCH(CH.sub.3).sub.2 H 3 11.0 Dark Brown      OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3 OCH(CH.sub.3).sub.2 H 79 OCH(CH.sub.3).sub.2 OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 H 3 18.9 " OCH(CH.sub.3).sub.2 OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 H 80 OCH(CH.sub.3).sub.2 OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 H 3 15.3 " OCH(CH.sub.3).sub.2 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 H       81      ##STR33##       OCH.sub.2 (CH.sub.2).sub.3       CH.sub.3 H 3 21.2 "      ##STR34##       OCH.sub.2 (CH.sub.2).sub. 3 CH.sub.3 H       82      ##STR35##       OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3 H 3 12.3 "      ##STR36##       OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 H  83 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3       ##STR37##       H 3 14.3 " OCH.sub.2 (CH.sub.2).sub.3       CH.sub.3      ##STR38##       H   84 OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3      ##STR39##       H 3 10.6 " OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3      ##STR40##       H  85 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      H 3 18.7 " OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 H 86 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 H 3 14.5 Dark Brown OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 H 87 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.2 CH(CH.sub.3).sub.2 H 3 19.6 " OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 H 88 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 H 3 12.8 " OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2       CH(CH.sub.3).sub.2 H 89 OC(CH.sub.3).sub.3 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 H 3 19.3 " OC(CH.sub.3).sub.3 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 H 90 OC(CH.sub.3).sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 H 3      15.5 " OC(CH.sub.3).sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 H 91      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OC(CH.sub. 3).sub.3 H 3 18.2 "      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OC(CH.sub.3).sub.3 H 92 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 OC(CH.sub.3).sub.3 H 3 11.1 " OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3OC(CH.sub.3).sub.3 H 93 OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H 3 14.7      " OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 H 94 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.4 CH.sub.3 H 3 9.3 Dark Brown OCH.sub.2 (CH.sub.2).sub.4      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 H 95 OCH.sub.2       (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 H 3 7.6 " O      CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 H      96 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 H 3 6.3 " OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 H 97 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.3 OCH.sub.3 3 11.6 " OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.3 OCH.sub.3 98 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.3      OCH.sub.3 3 8.7 " OCH.sub.2 (CH.sub.2).sub.4       CH.sub.3 OCH.sub.3 OCH.sub.3 99 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3      OCH.sub.3 OCH.sub.3 3 7.9 " OCH.sub.2 (CH.sub.2).sub.5       CH.sub.3 OCH.sub.3 OCH.sub.3 100 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      OCH.sub.3 OCH.sub.3 3 15.7 " OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      OCH.sub.3 OCH.sub.3 101 OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 3 19.2 " OCH.sub.3 OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 102      OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4      CH.sub.3 3 16.3 Dark Brown OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 O      CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 103 OCH.sub.3 OCH.sub.2       (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 3 13.3 "      OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5      CH.sub.3 104 OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 3 7.5 "OCH.sub.3 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 105 OCH(CH.sub.3).sub.2      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      3 12.6 " OCH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2 ).sub.3 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 106 OCH(CH.sub.3).sub.2 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 3 8.7 "      OCH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 107 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2 3 10.8 " OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2 108      OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3 OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2 3 7.1 " OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 OCH(CH.sub.3).sub.2 OCH(CH.sub.3).sub. 2  109       ##STR41##       OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      3 10.8 "       ##STR42##       OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3       110      ##STR43##       OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      3 9.4 Dark Brown       ##STR44##       OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3       111 OCH.sub.2 (CH.sub.2).sub.3       CH.sub.3      ##STR45##       ##STR46##       3 4.7 " OCH.sub.2 (CH.sub.2).sub.3       CH.sub.3      ##STR47##       ##STR48##        112 OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3      ##STR49##       ##STR50##       3 3.2 " OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3      ##STR51##       ##STR52##        113 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 313.9 " OCH.sub.2 CH(CH.sub.3).sub.2 O      CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      114 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 3 10.1 " OCH.sub.2       CH(CH.sub.3).sub.2 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 115 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 CH(CH.sub.3).sub.2 3 5.6 "      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2      OCH.sub.2 CH(CH.sub.3).sub.2 116 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 CH(CH.sub.3).sub.2 3 4.4 "      OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH(CH.sub.3).sub.2      OCH.sub.2 CH(CH.sub.3).sub.2 117 OC(CH.sub.3).sub.3 OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 3 12.4 "      OC(CH.sub.3).sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 118 OC(CH.sub.3).sub.3 OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 3 10.6      Dark Brown OC(CH.sub.3).sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 119 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 OC(CH.sub.3).sub.3 OC(CH.sub.3).sub.3 3 3.3 " OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 OC(CH.sub.3).sub.3 OC(CH.sub.3 ).sub.3 120      OCH.sub.2 (CH.sub.2).sub.6       CH.sub.3 OC(CH.sub.3).sub.3 OC(CH.sub.3).sub.3 3 2.1 " OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 OC(CH.sub.3).sub.3 OC(CH.sub.3).sub.3 121      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 3 9.8 " OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 122 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 3 8.6 "      OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 123 OCH.sub.2 (CH.sub.2).sub.5      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5      CH.sub.3 3 4.7 " OCH.sub.2 (CH.sub.2 ).sub.5 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 124      OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 3 5.2 " OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 125 H CH.sub.3 CH.sub.3 3 55.0 Reddish Brown H CH.sub.3      CH.sub.3 126 OCH.sub.3 CH.sub.3 CH.sub.3 3 37.3 Reddish Brown OCH.sub.3      CH.sub.3 CH.sub.3 127 OC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 3 35.7 "      OC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 128 OCH.sub.2 CH.sub.2 CH.sub.3      CH.sub.3 CH.sub.3 3 32.2 " OCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3      129 OCH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 3 29.3 "  OCH(CH.sub.3).sub.2      CH.sub.3 CH.sub.3 130 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3      CH.sub.3 3 40.5 " OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CH.sub.3      131       ##STR53##       CH.sub.3 CH.sub.3 3 33.6 "       ##STR54##       CH.sub.3 CH.sub.3  132 OCH.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 3      31.6 " OCH.sub.2       CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 133 OC(CH.sub.3).sub.3 CH.sub.3      CH.sub.3 3 27.7 " OC(CH.sub.3).sub.3 CH.sub.3 CH.sub.3 134 OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3 38.5 Brown OCH.sub.2      (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CH.sub.3 135 OCH.sub.2       (CH.sub.2).sub.4 CH.sub.3 CH.sub.3 CH.sub.3 3 35.4 " OCH.sub. 2      (CH.sub.2).sub.4 CH.sub.3 CH.sub.3 CH.sub.3 136 OCH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.3 CH.sub.3 3 31.7 " OCH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.3 CH.sub.3 137 OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 CH.sub.3 CH.sub.3 3 28.1 " OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 CH.sub.3 CH.sub.3 138 OCH.sub.3 C.sub.2      H.sub.5 C.sub.2 H.sub.5 3 39.9 Reddish Brown OCH.sub.3 C.sub.2 H.sub.5      C.sub.2 H.sub.5 139 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2      CH.sub.2 CH.sub.3 3 17.6 " OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2      CH.sub.2 CH.sub.3 140 OCH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3      CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 3 30.1 Brown OCH.sub.3 CH.sub.2      (CH.sub.2).sub.2 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 141      OCH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2 (CH.sub.2).sub.3      CH.sub.3 3 26.3 " OCH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2      (CH.sub.2).sub.3 CH.sub.3 142 OCH.sub.3 CH.sub.2 (CH.sub.2).sub.4      CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 3 23.7 Brown OCH.sub.3      CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3      143 OCH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 3 18.8 Dark Brown OCH.sub.3 CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 144      OCH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6      CH.sub.3 3 15.6 " OCH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 CH.sub.2      (CH.sub.2).sub.6 CH.sub.3 145 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2      H.sub.5 3 30.0 Brown OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5      146 OCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2      CH.sub.2 CH.sub.3 3 17.9 " OCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2      CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 147 OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2      CH.sub.3 3 24.9 Dark Brown OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.2      (CH.sub.2).sub.2 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 148      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3      CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 3 23.1 " OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2 (CH.sub.2).sub.3      CH.sub.3 149 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 CH.sub.2 (CH.sub.2      ).sub.4 CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 3 18.4 " OCH.sub.2      (CH.sub.2).sub.4 CH.sub.3 CH(CH.sub.2).sub.4 CH.sub.3 CH.sub.2       (CH.sub.2).sub.4 CH.sub.3 150 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3      CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 3      19.5 Dark Brown OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 151      OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3      CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 3 11.8 " OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6      CH.sub.3 152 H CH.sub.3 H 3 27.2 Reddish Brown H H CH.sub.3 153 CH.sub.3 O      CH.sub.3 OCH.sub.3 3 23.7 Dark Brown CH.sub.3 OCH.sub.3  OCH.sub.3 154      C.sub.2 H.sub.5 OCH.sub.3 OCH.sub.3 3 25.8 " C.sub.2 H.sub.5 OCH.sub.3      OCH.sub.3 155 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 3 20.6 "      CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 156 CH(CH.sub.3).sub.2      OCH.sub.3 OCH.sub.3 3 17.5 " CH(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 157      CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3 3 22.7 " CH.sub.2      (CH.sub.2).sub.2 CH.sub.3 OCH.sub.3 OCH.sub.3       158      ##STR55##       OCH.sub.3 OCH.sub.3 3 17.6 Dark Brown       ##STR56##       OCH.sub.3 OCH.sub.3  159 CH.sub.2       CH(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 3 11.1 " CH.sub.2       CH(CH.sub.3).sub.2 OCH.sub.3 OCH.sub.3 160 C(CH.sub.3).sub.3 OCH.sub.3      OCH.sub.3 3 8.9 " C(CH.sub.3).sub.3 OCH.sub.3 OCH.sub.3 161 CH.sub.2      (CH.sub.2).sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 3 19.3 " CH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH.sub.3 OCH.sub.3 162 CH.sub.2       (CH.sub.2).sub.4 CH.sub.3 OCH.sub.3 OCH.sub.3 3 16.5 " CH.sub.2      (CH.sub.2).sub.4 CH.sub.3 OCH.sub.3 OCH.sub.3 163 CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 OCH.sub.3 OCH.sub.3 3 14.9 " CH.sub.2      (CH.sub.2).sub.5 CH.sub.3 OCH.sub.3 OCH.sub.3 164 CH.sub.2       (CH.sub.2).sub.6 CH.sub.3 OCH.sub.3 OCH.sub.3 3 13.0 " CH.sub.2      (CH.sub.2).sub.6 CH.sub.3 OCH.sub.3 OCH.sub.3 165 CH.sub.3 OC.sub.2      H.sub.5 OC.sub.2 H.sub.5 3 24.2 " CH.sub.3 OC.sub.2 H.sub.5 OC.sub.2      H.sub.5 166 CH.sub.3 OCH.sub.2 CH.sub. 2 CH.sub.3 OCH.sub.2 CH.sub.2      CH.sub.3 3 17.5 Dark Brown CH.sub.3 OCH.sub.2 CH.sub.2       CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 167 CH.sub.3 OCH(CH.sub.3).sub.2      OCH(CH.sub.3).sub.2 3 14.4 " CH.sub.3 OCH(CH.sub.3).sub.2 OCH(CH.sub.3).s      ub.2 168 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 3 20.8 " CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3       169 CH.sub.3      ##STR57##       ##STR58##       3 15.3 " CH.sub.3       ##STR59##       ##STR60##        170 CH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2 CH(CH.sub.3).sub.2      3 16.7 " CH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub. 2       CH(CH.sub.3).sub.2 171 CH.sub.3 OC(CH.sub.3).sub.3 OC(CH.sub.3).sub.3 3      12.3 " CH.sub.3 OC(CH.sub.3).sub.3 OC(CH.sub.3).sub.3 172 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3      3 19.6 " CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 173 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 3 17.8 " CH.sub.3 OCH.sub.2      (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 174      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5      CH.sub.3 3 16.0 Dark Brown CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 175 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 3 13.1 "  C      H.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 176 C.sub.2 H.sub.5 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 3 24.6 "      C.sub.2 H.sub.5 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 177 CH.sub.2 CH.sub.2      CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 3 21.7      " CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.2      CH.sub.2 CH.sub.3 178 CH.sub.2 (CH.sub.2)CH.sub.3 OCH.sub.2       (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 3 18.7 "      CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.2 CH.sub.3 179 CH.sub.2 (CH.sub.2).sub.3      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3      CH.sub.3 3 16.2 " CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.3 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 180      CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 3 16.6 " CH.sub.2 (CH.sub.2).sub.4      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.4      CH.sub.3 181 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2       (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 3 15.5 "      CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3      OCH.sub.2 (CH.sub.2).sub.5 CH.sub.3 182 CH.sub.2 (CH.sub.2).sub.6      CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6      CH.sub.3 3 11.7 Dark Brown CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2      (CH.sub.2).sub.6 CH.sub.3 OCH.sub.2 (CH.sub.2).sub.6 CH.sub.3 183 C.sub.      2 H.sub.5  H H 3 48.3 " C.sub.2 H.sub.5 H H 184 CH.sub.2       (CH.sub.2).sub.6 CH.sub.3 H H 3 37.3 Black CH.sub.2 (CH.sub.2).sub.6      CH.sub.3 H H 185 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 5 65.3 Brown C.sub.2      H.sub.5 CH.sub.3 CH.sub.3 186 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3      CH.sub.3 5 59.2 " CH.sub.2 CH.sub.2 CH.sub.3  CH.sub.3 CH.sub.3 187      CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 5 43.2 " CH(CH.sub.3).sub.2      CH.sub.3 CH.sub.3 188 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3      CH.sub.3 5 54.4 " CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CH.sub.3      189       ##STR61##       CH.sub.3 CH.sub.3 5 37.0 "       ##STR62##       CH.sub.3 CH.sub.3  190 CH.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 5      40.3 Brown CH.sub.2       CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 191 C(CH.sub.3).sub.3 CH.sub.3      CH.sub.3 5 28.7 " C(CH.sub.3).sub.3 CH.sub.3 CH.sub.3 192 CH.sub.2      (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CH.sub.3 5 51.2 " CH.sub.2       (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CH.sub.3 193 CH.sub.2       (CH.sub.2).sub.4 CH.sub.3 CH.sub.3 CH.sub.3 5 48.7 " CH.sub.2       (CH.sub.2).sub.4 CH.sub.3 CH.sub.3 CH.sub.3 194 CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.3 CH.sub.3 5 36.5 " CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.3 CH.sub.3 195 CH.sub.2       (CH.sub.2).sub.6 CH.sub.3 CH.sub.3 CH.sub.3 5 21.9 " CH.sub.2       (CH.sub.2).sub. 6 CH.sub.3 CH.sub.3 CH.sub.3 196 CH.sub.3 C.sub.2      H.sub.5 C.sub.2 H.sub.5 5 63.5 " CH.sub.3 C.sub.2 H.sub.5 C.sub.2      H.sub.5 197 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2      CH.sub.3 5 52.4 " CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2      CH.sub.3 198 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.2      (CH.sub.2).sub.2 CH.sub.3 5 47.3 Brown CH.sub.3 CH.sub.2       (CH.sub.2).sub.2 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 199      CH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2 (CH.sub.2).sub.3      CH.sub.3 5 39.2 " CH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2      (CH.sub.2).sub.3 CH.sub.3 200 CH.sub.3 CH.sub.2 (CH.sub.2).sub.4      CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 5 28.9 " CH.sub. 3 CH.sub.2      (CH.sub.2).sub.4 CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 201      CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 (CH.sub.2).sub.5      CH.sub.3 5 19.8 " CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2      (CH.sub.2).sub.5 CH.sub.3 202 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6      CH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 5 18.2 " CH.sub.3 CH.sub.2      (CH.sub.2).sub.6 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 203 C.sub.2      H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 5 60.2 " C.sub.2 H.sub.5 C.sub.2      H.sub.5 C.sub.2 H.sub.5 204 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2      CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 5 55.6 " CH.sub.2 CH.sub.2 CH.sub.3      CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 205 CH.sub.2      (CH.sub. 2).sub.2 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.2      (CH.sub.2).sub.2 CH.sub.3 5 43.3 " CH.sub.2 (CH.sub.2).sub.2 CH.sub.3      CH.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.2 (CH.sub.2).sub.2 CH.sub.3      206 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2 (CH.sub.2).sub.3      CH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 5 38.0 Brown CH.sub.2      (CH.sub.2).sub.3 CH.sub.3 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.2      (CH.sub.2).sub.3 CH.sub.3 207 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3      CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 5      26.8 " CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 CH.sub.2 (CH.sub.2).sub.4      CH.sub.3 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 208 CH.sub.2       (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2      (CH.sub.2).sub.5 CH.sub.3 5 13.2 " CH.sub.2 (CH.sub.2).sub.5 CH.sub.3      CH.sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 (CH.sub.2).sub.5 CH.sub.3      209 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6      CH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 5 11.3 " CH.sub.2       (CH.sub.2).sub.6 CH.sub.3 CH.sub.2 (CH.sub.2).sub.6 CH.sub.3 CH.sub.2      (CH.sub.2).sub.6       CH.sub.3

                                      TABLE 1-2                                    __________________________________________________________________________                   Elementary Analysis                                              Example                                                                             Mass Spectrum     C:H:N (%)       Visible Spectrum [DMF]                  No.  Calcd.                                                                              Found                                                                              Formula  Calcd.  Found   (nm)                                    __________________________________________________________________________     6    585.6                                                                               585 C.sub.34 H.sub.30 N.sub.4 O.sub.2.Co                                                    69.74:5.16:9.57                                                                        69.61:5.22:9.56                                                                        380(s)*.sup.(1), 397, 429(s),                                                  522                                     7    613.6                                                                               613 C.sub.36 H.sub.34 N.sub.4 O.sub.2.Co                                                    70.47:5.59:9.13                                                                        69.99:5.65:8.98                                                                        380(s), 397, 429(s),                                                           522                                     8    557.5                                                                               557 C.sub.32 H.sub.26 N.sub.4 O.sub.2.Co                                                    68.94:4.70:10.05                                                                       69.04:4.70:10.01                                                                       388, 419, 438,                                                                 522                                     9    585.6                                                                               585 C.sub.34 H.sub.30 N.sub.4 O.sub.2.Co                                                    69.74:5.16:9.57                                                                        69.66:5.23:9.47                                                                        388, 419, 438,                                                                 522                                     10   613.6                                                                               613 C.sub.36 H.sub.34 N.sub.4 O.sub.2.Co                                                    70.47:5.59:9.13                                                                        70.58:5.63:9.01                                                                        380(s), 397, 429(s),                                                           522                                     11   641.7                                                                               641 C.sub.38 H.sub.38 N.sub.4 O.sub.2.Co                                                    71.13:5.97:8.73                                                                        71.02:5.88:8.65                                                                        380(s), 397, 429(s),                                                           522                                     12   641.7                                                                               641 C.sub.38 H.sub.38 N.sub.4 O.sub.2.Co                                                    71.13:5.97:8.73                                                                        71.21:6.05:8.59                                                                        380(s), 397, 429(s),                                                           522                                     13   617.6                                                                               617 C.sub.34 H.sub.30 N.sub.4 O.sub.4.Co                                                    66.12:4.90:9.07                                                                        65.97:5.02:9.01                                                                        382, 426, 453,                                                                 ˜520*.sup.(2)                     14   613.6                                                                               613 C.sub.36 H.sub.34 N.sub.4 O.sub.2.Co                                                    70.47:5.57:9.13                                                                        70.56:5.70:9.10                                                                        388 419, 438,                                                                  522                                     15   641.7                                                                               641 C.sub.38 H.sub.38 N.sub.4 O.sub.2.Co                                                    71.13:5.97:8.73                                                                        71.11:6.04:8.82                                                                        388, 419, 437,                                                                 522                                     16   673.7                                                                               673 C.sub.38 H.sub.38 N.sub.4 O.sub.4.Co                                                    67.75:5.69:8.32                                                                        67.97:5.52:8.30                                                                        382, 427, 454,                                                                 ˜520                              17   729.7                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.28:6.40:7.52                                                                        383, 429, 454,                                                                 ˜520                              18   785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.51:7.02:7.00                                                                        383, 428, 454,                                                                 ˜520                              19   617.6                                                                               617 C.sub.34 H.sub.30 N.sub.4 O.sub.4.Co                                                    66.12:4.90:9.07                                                                        66.22:4.79:9.13                                                                        388(s), 399, 420(s),                                                           444(s), 522                             20   645.6                                                                               645 C.sub.36 H.sub.34 N.sub.4 O.sub.4.Co                                                    66.78:5.31:8.68                                                                        67.07:5.41:8.62                                                                        388(s), 399, 420(s),                                                           444(s), 522                             21   673.7                                                                               673 C.sub.38 H.sub.38 N.sub.4 O.sub.4.Co                                                    67.75:5.67:8.32                                                                        68.01:5.55:8.43                                                                        388(s), 399, 420(s),                                                           443(s), 522                             22   673.7                                                                               673 C.sub.38 H.sub.38 N.sub.4 O.sub.4.Co                                                    67.75:5.67:8.32                                                                        68.01:5.55:8.43                                                                        388(s), 399, 420(s),                                                           443(s), 521                             23   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.34:5.97:7.87                                                                        388(s), 399, 420(s),                                                           443(s), 521                             24   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.62:5.95:7.90                                                                        388(s), 399, 420(s),                                                           443(s), 521                             25   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.58:5.93:8.10                                                                        388(s), 399, 420(s),                                                           443(s), 521                             26   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.35:6.11:8.03                                                                        388(s), 399, 420(s),                                                           443(s), 521                             27   733.7                                                                               733 C.sub.40 H.sub.42 N.sub.4 O.sub.6.Co                                                    65.48:5.77:7.64                                                                        65.59:5.65:7.70                                                                        384, 395(s), 430,                                                              457, ˜525                         28   789.8                                                                               789 C.sub.44 H.sub. 50 N.sub.4 O.sub.6.Co                                                   66.91:6.38:7.09                                                                        66.83:6.36:7.12                                                                        384, 395(s), 430,                                                              457, ˜524                         29   789.8                                                                               789 C.sub.44 H.sub.50 N.sub.4 O.sub.6.Co                                                    66.91:6.38:7.09                                                                        67.12:6.35:6.87                                                                        384, 395(s), 430,                                                              457, ˜524                         30   845.9                                                                               845 C.sub.48 H.sub.58 N.sub.4 O.sub.6.Co                                                    68.16:6.91:6.62                                                                        68.06:7.11:6.69                                                                        384, 395(s), 429,                                                              458, ˜525                         31   845.9                                                                               845 C.sub.48 H.sub.58 N.sub.4 O.sub.6.Co                                                    68.16:6.91:6.62                                                                        68.11:6.82:6.79                                                                        384, 395(s), 430                                                               457, ˜525                         32   845.9                                                                               845 C.sub.48 H.sub.58 N.sub.4 O.sub.6.Co                                                    68.16:6.91:6.62                                                                        68.07:6.98:6.83                                                                        384, 395(s), 430,                                                              458, ˜525                         33   645.6                                                                               645 C.sub.36 H.sub.34 N.sub.4 O.sub.4.Co                                                    66.98:5.31:8.68                                                                        66.90:5.41:8.61                                                                        388(s), 399, 420(s),                                                           444(s), 523                             34   673.7                                                                               673 C.sub.38 H.sub.38 N.sub.4 O.sub.4.Co                                                    67.75:5.69:8.32                                                                        67.51:5.67:8.19                                                                        388(s), 399, 420(s),                                                           443(s), 522                             35   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.78                                                                        68.33:6.21:8.08                                                                        388(s), 399, 420(s),                                                           443(s), 522                             36   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.78                                                                        68.63:5.92:7.84                                                                        388(s), 399, 420(s),                                                           443(s), 522                             37   729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.30:6.48:7.57                                                                        388(s), 399, 420(s),                                                           443(s), 522                             38   705.7                                                                               705 C.sub.38 H.sub.38 N.sub.4 O.sub.6.Co                                                    64.68:5.43:7.94                                                                        64.61:5.53:7.86                                                                        384, 395(s), 430,                                                              457, ˜525                         39   761.8                                                                               761 C.sub.42 H.sub.46 N.sub.4 O.sub.6.Co                                                    66.22:6.09:7.35                                                                        66.19:6.20:7.44                                                                        384, 395(s), 431,                                                              456, ˜525                         40   817.9                                                                               817 C.sub.46 H.sub.54 N.sub.4 O.sub.6.Co                                                    67.55:6.66:6.85                                                                        67.63:6.85:6.91                                                                        384, 395(s), 430,                                                              458, ˜524                         41   874.0                                                                               873 C.sub.50 H.sub.62 N.sub.4 O.sub.6.Co                                                    68.71:7.15:6.41                                                                        68.55:7.08:6.32                                                                        384, 395(s), 429,                                                              458, ˜525                         42   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.53:6.00:7.91                                                                        388(s), 399, 420(s),                                                           443(s), 522                             43   729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.06:6.20:7.70                                                                        388(s), 399, 420(s),                                                           442(s), 521                             44   757.8                                                                               757 C.sub.44 H.sub.50 N.sub.4 O.sub.4.Co                                                    69.74:6.65:7.39                                                                        69.87:6.54:7.45                                                                        388(s), 399, 420(s),                                                           442(s), 521                             45   733.7                                                                               733 C.sub.40 H.sub.42 N.sub.4 O.sub.6.Co                                                    65.48:5.77:7.64                                                                        65.32:5.91:7.60                                                                        384, 395(s), 430,                                                              457, ˜525                         46   789.8                                                                               789 C.sub.44 H.sub.50 N.sub.4 O.sub.6.Co                                                    66.91:6.38:7.09                                                                        67.09:6.20:7.13                                                                        384, 395(s), 431,                                                              456, ˜526                         47   845.7                                                                               845 C.sub.48 H.sub.58 N.sub.4 O.sub.6.Co                                                    68.16:6.91:6.62                                                                        67.97:7.01:6.77                                                                        384, 396(s), 431,                                                              458, ˜524                         48   902.1                                                                               901 C.sub.52 H.sub.66 N.sub.4 O.sub.6.Co                                                    69.24:7.37:6.21                                                                        69.11:7.53:6.15                                                                        384, 396(s), 429,                                                              459, ˜525                         49   673.7                                                                               673 C.sub.38 H.sub.38 N.sub.4 O.sub.4.Co                                                    67.75:5.67:8.32                                                                        67.88:5.55:8.40                                                                        388(s), 399, 420(s),                                                           443(s), 522                             50   729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        68.98:6.39:7.75                                                                        388(s), 399, 420(s),                                                           443(s), 521                             51   733.7                                                                               733 C.sub.40 H.sub.42 N.sub.4 O.sub.6.Co                                                    65.48:5.77:7.64                                                                        65.61:5.67:7.55                                                                        384, 395(s), 430,                                                              457, ˜524                         52   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.58:6.15:7.83                                                                        388(s), 399, 420(s),                                                           442(s), 521                             53   729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.31:6.38:7.78                                                                        388(s), 399, 420(s),                                                           442(s), 521                             54   757.8                                                                               757 C.sub.44 H.sub.50 N.sub.4 O.sub.4.Co                                                    69.74:6.65:7.39                                                                        69.97:6.60:7.33                                                                        388(s), 399, 420(s),                                                           442(s), 521                             55   785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.20:6.76:7.33                                                                        388(s), 399, 420(s),                                                           442(s), 521                             56   761.8                                                                               761 C.sub.42 H.sub.46 N.sub.4 O.sub.6.Co                                                    66.22:6.09:7.35                                                                        66.19:6.01:7.55                                                                        383, 394(s), 430,                                                              457, ˜525                         57   817.9                                                                               817 C.sub.46 H.sub.54 N.sub.4 O.sub.6.Co                                                    67.55:6.66:6.85                                                                        67.85:6.55:6.73                                                                        384, 395(s), 930,                                                              457, ˜525                         58   874.0                                                                               873 C.sub.50 H.sub.62 N.sub.4 O.sub.6.Co                                                    68.71:7.15:6.41                                                                        68.82:7.01:6.33                                                                        384, 396(s), 431,                                                              458, ˜523                         59   930.1                                                                               929 C.sub.54 H.sub.70 N.sub.4 O.sub.6.Co                                                    69.73:7.59:6.02                                                                        69.78:7.53:6.21                                                                        385, 396(s), 429,                                                              459, ˜524                         60   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.29:6.15:8.06                                                                        388(s), 399, 420(s),                                                           444(s), 522                             61   785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.48:7.05:6.95                                                                        388(s), 399, 420(s),                                                           443(s), 522                             62   761.8                                                                               761 C.sub.42 H.sub.46 N.sub.4 O.sub.6.Co                                                    66.22:6.09:7.35                                                                        66.34:5.98:7.29                                                                        384, 395(s), 430,                                                              457, ˜525                         63   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.33:6.05:8.12                                                                        388(s), 399, 420(s),                                                           443(s), 522                             64   785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.25:7.07:7.01                                                                        388(s), 399, 420(s),                                                           443(s), 522                             65   761.8                                                                               761 C.sub.42 H.sub.46 N.sub.4 O.sub.6.Co                                                    66.22:6.09:7.35                                                                        66.18:6.04:7.44                                                                        384, 395(s), 430,                                                              457, ˜525                         66   641.7                                                                               641 C.sub.38 H.sub.38 N.sub.4 O.sub.2.Co                                                    71.13:5.97:8.73                                                                        70.95:6.11:8.67                                                                        380(s), 397, 429(s),                                                           522                                     67   701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.47:6.03:7.98                                                                        68.63:5.97:8.06                                                                        388(s), 399, 420(s),                                                           443(s), 522                             68   761.8                                                                               761 C.sub.42 H.sub.46 N.sub.4 O.sub.6.Co                                                    66.22:6.09:7.35                                                                        66.34:5.96:7.43                                                                        384, 395(s), 430,                                                              457, ˜524                         69   669.7                                                                               669 C.sub.40 H.sub.42 N.sub.4 O.sub.2.Co                                                    71.74:6.32:8.37                                                                        71.83:6.30:8.34                                                                        380(s), 397, 429(s),                                                           522                                     70   753.9                                                                               753 C.sub.46 H.sub.54 N.sub.4 O.sub.2.Co                                                    73.29:7.22:7.43                                                                        73.36:7.19:7.37                                                                        380(s), 397, 429(s),                                                           522                                     71   669.7                                                                               669 C.sub.40 H.sub.42 N.sub.4 O.sub.2.Co                                                    71.74:6.32:8.37                                                                        71.85:6.29:8.31                                                                        388, 419, 437,                                                                 522                                     72   753.9                                                                               753 C.sub.46 H.sub.54 N.sub.4 O.sub.2.Co                                                    73.29:7.22:7.43                                                                        73.35:7.16:7.45                                                                        389, 419, 437,                                                                 521                                     73   729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.05:6.32:7.71                                                                        399, 420(s), 442(s),                                                           388(s), 522                             74   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.77:7.23:6.90                                                                        399, 420(s), 442(s),                                                           388(s), 521                             75   729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.21:6.40:7.58                                                                        388(s), 399, 420(s),                                                           442(s), 523                             76   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.76:7.23:6.92                                                                        388(s), 399, 420(s),                                                           441(s), 522                             77   785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.41:6.85:7.09                                                                        399, 420(s), 443(s),                                                           388(s), 522                             78   870.1                                                                               869 C.sub.52 H.sub.66 N.sub.4 O.sub.4.Co                                                    71.79:7.65:6.44                                                                        71.87:7.59:6.51                                                                        399, 420(s), 443(s),                                                           388(s), 522                             79   785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.42:6.85:7.08                                                                        388(s), 399, 420(s),                                                           442(s), 522                             80   870.1                                                                               869 C.sub.52 H.sub.66 N.sub.4 O.sub.4.Co                                                    71.79:7.65:6.44                                                                        71.92:7.58:6.41                                                                        388(s), 399, 420(s),                                                           442(s), 522                             81   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.92:7.07:6.93                                                                        388(s), 399, 420(s),                                                           442(s), 522                             82   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.18:7.99:6.17                                                                        388(s), 399, 420(s),                                                           442(s), 522                             83   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.94:7.09:6.93                                                                        388(s), 399, 420(s),                                                           442(s), 521                             84   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.33:7.78:6.12                                                                        388(s), 399, 420(s),                                                           442(s), 522                             85   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.95:7.06:6.93                                                                        388(s), 399, 420(s),                                                           442(s), 522                             86   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.34:7.91:6.11                                                                        388(s), 399, 420(s),                                                           441(s), 522                             87   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.72:7.23:6.94                                                                        388(s), 399, 420(s),                                                           441(s), 521                             88   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.30:7.79:6.18                                                                        388(s), 399, 420(s),                                                           442(s), 522                             89   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.95:7.07:6.93                                                                        389(s), 399, 421(s),                                                           443(s), 523                             90   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.10:7.93:6.29                                                                        388(s), 399, 420(s),                                                           442(s), 522                             91   813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.91:7.11:6.82                                                                        388(s), 399, 420(s),                                                           443(s), 522                             92   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.32:7.77:6.21                                                                        388(s), 399, 420(s),                                                           442(s), 521                             93   842.0                                                                               841 C.sub.50 H.sub.62 N.sub.4 O.sub.4.Co                                                    71.32:7.42:6.65                                                                        71.44:7.36:6.58                                                                        388(s), 399, 420(s),                                                           442(s), 522                             94   898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.29:7.78:6.19                                                                        388(s), 399, 420(s),                                                           442(s), 521                             95   954.2                                                                               953 C.sub.58 H.sub.78 N.sub.4 O.sub.4.Co                                                    73.01:8.24:5.87                                                                        73.14:8.15:5.78                                                                        388(s), 399, 420(s),                                                           441(s), 521                             96   1010.3                                                                              1009                                                                               C.sub.62 H.sub.86 N.sub.4 O.sub.4.Co                                                    73.71:8.58:5.55                                                                        73.65:8.63:5.48                                                                        388(s), 399, 420(s),                                                           441(s), 522                             97   789.8                                                                               789 C.sub.44 H.sub.50 N.sub.4 O.sub.6.Co                                                    66.91:6.38:7.09                                                                        67.04:6.31:7.03                                                                        383, 395(s), 430,                                                              457, 525                                98   817.9                                                                               817 C.sub.46 H.sub.54 N.sub.4 O.sub.6.Co                                                    67.55:6.66:6.85                                                                        67.54:6.58:6.92                                                                        383, 394(s), 430,                                                              457, 525                                99   845.9                                                                               845 C.sub.48 H.sub.58 N.sub.4 O.sub.6.Co                                                    68.15:6.91:6.62                                                                        68.32:6.82:6.57                                                                        383, 395(s), 429,                                                              457, 526                                100  874.0                                                                               873 C.sub.50 H.sub.62 N.sub.4 O.sub.6.Co                                                    68.71:7.15:6.41                                                                        68.63:7.17:6.50                                                                        383, 396(s), 429,                                                              457, 526                                101  902.1                                                                               901 C.sub.52 H.sub.66 N.sub.4 O.sub.6.Co                                                    69.24:7.38:6.21                                                                        69.40:7.36:6.18                                                                        384, 396(s), 429,                                                              457, 525                                102  958.2                                                                               957 C.sub.56 H.sub.74 N.sub.4 O.sub.6.Co                                                    70.20:7.78:5.85                                                                        70.08:7.84:5.92                                                                        383, 396(s), 430,                                                              457, 525                                103  1014.3                                                                              1013                                                                               C.sub.60 H.sub.82 N.sub.4 O.sub.6.Co                                                    71.05:8.15:5.52                                                                        71.21:8.08:5.44                                                                        384, 395(s), 429,                                                              458, 525                                104  1070.4                                                                              1069                                                                               C.sub.64 H.sub.90 N.sub.4 O.sub.6.Co                                                    71.82:8.48:5.23                                                                        71.88:8.55:5.12                                                                        384, 396(s), 429,                                                              459, 525                                105  958.2                                                                               957 C.sub.56 H.sub.74 N.sub.4 O.sub.6.Co                                                    70.20:7.78:5.85                                                                        70.19:7.67:5.95                                                                        383, 396(s), 428,                                                              457, 524                                106  1126.5                                                                              1125                                                                               C.sub.68 H.sub.98 N.sub.4 O.sub.6.Co                                                    72.50:8.77:4.97                                                                        72.43:8.68:5.13                                                                        385, 396(s), 429,                                                              459, 525                                107  902.1                                                                               901 C.sub.52 H.sub.66 N.sub.4 O.sub.6 .Co                                                   69.24:7.38:6.21                                                                        69.33:7.51:6.08                                                                        384, 396(s), 430,                                                              458, 525                                108  986.2                                                                               985 C.sub.58 H.sub.78 N.sub.4 O.sub.6.Co                                                    70.64:7.97:5.68                                                                        70.75:8.12:5.56                                                                        384, 396(s), 430,                                                              457, 525                                109  986.2                                                                               985 C.sub.58 H.sub.78 N.sub.4 O.sub.6.Co                                                    70.64:7.97:5.68                                                                        70.73:8.03:5.72                                                                        384, 396(s), 430,                                                              458, 525                                110  1154.5                                                                              1153                                                                               C.sub.70 H.sub.102 N.sub.4 O.sub.6.Co                                                   72.82:8.91:4.85                                                                        72.78:9.11:4.72                                                                        384, 396(s), 429,                                                              459, 525                                111  958.2                                                                               957 C.sub.56 H.sub.74 N.sub.4 O.sub.6.Co                                                    70.20:7.78:5.85                                                                        70.12:7.93:5.77                                                                        385, 395(s), 429,                                                              458, 525                                112  1042.3                                                                              1041                                                                               C.sub.62 H.sub.86 N.sub.4 O.sub.6.Co                                                    71.44:8.32:5.38                                                                        71.40:8.43:5.32                                                                        385, 396(s), 429,                                                              459, 525                                113  986.2                                                                               985 C.sub.58 H.sub.78 N.sub.4 O.sub.6.Co                                                    70.64:7.97:5.68                                                                        70.59:7.82:5.73                                                                        384, 396(s), 429,                                                              459, 525                                114  1154.5                                                                              1153                                                                               C.sub.70 H.sub.102 N.sub.4 O.sub.6.Co                                                   72.82:8.91:4.85                                                                        72.76:9.03:4.82                                                                        384, 395(s), 429,                                                              458, 525                                115  958.2                                                                               957 C.sub.56 H.sub.74 N.sub. 4 O.sub.6.Co                                                   70.20:7.78:5.85                                                                        70.25:7.82:5.74                                                                        385, 396(s), 429,                                                              459, 525                                116  1042.3                                                                              1041                                                                               C.sub.62 H.sub.86 N.sub.4 O.sub.6.Co                                                    71.44:8.32:5.38                                                                        71.32:8.36:5.43                                                                        384, 395(s), 429,                                                              458, 525                                117  986.2                                                                               985 C.sub.58 H.sub.78 N.sub.4 O.sub.6.Co                                                    70.64:7.97:5.68                                                                        70.70:7.86:5.72                                                                        383, 396(s), 428,                                                              457, 524                                118  1154.5                                                                              1153                                                                               C.sub.70 H.sub.102 N.sub.4 O.sub.6.Co                                                   72.82:8.91:4.85                                                                        72.87:8.98:4.72                                                                        384, 396(s), 429,                                                              459, 525                                119  958.2                                                                               957 C.sub.56 H.sub.74 N.sub.4 O.sub.6.Co                                                    70.20:7.78:5.85                                                                        70.17:7.74:5.81                                                                        384, 395(s), 430,                                                              457, 525                                120  1042.3                                                                              1041                                                                               C.sub.62 H.sub.86 N.sub.4 O.sub.6.Co                                                    71.44:8.32:5.38                                                                        71.62:8.25:5.33                                                                        383, 394(s), 430,                                                              457, 525                                121  1014.3                                                                              1013                                                                               C.sub.60 H.sub.82 N.sub.4 O.sub.6.Co                                                    71.05:8.15:5.52                                                                        70.97:8.22:5.57                                                                        384, 397(s), 429,                                                              459, 525                                122  1098.4                                                                              1097                                                                               C.sub.66 H.sub.94 N.sub.4 O.sub.6.Co                                                    72.17:8.63:5.10                                                                        72.32:8.55:5.02                                                                        384, 396(s), 430,                                                              458, 524                                123  1182.6                                                                              1181                                                                               C.sub.72 H.sub.106 N.sub.4 O.sub.6.Co                                                   73.13:9.04:4.74                                                                        73.22:8.97:4.70                                                                        385, 396(s), 429,                                                              459, 525                                124  1266.8                                                                              1265                                                                               C.sub.78 H.sub.118 N.sub.4 O.sub.6.Co                                                   73.96:9.39:4.42                                                                        74.11:9.27:4.46                                                                        385, 396(s), 429,                                                              459, 525                                125  553.6                                                                               553 C.sub.34 H.sub.30 N.sub.4.Co                                                            73.77:5.46:10.12                                                                       73.91:5.39:10.07                                                                       388, 419, 436(s),                                                              524                                     126  613.6                                                                               613 C.sub.36 H.sub.34 N.sub.4 O.sub.2.Co                                                    70.47:5.59:9.13                                                                        70.52:5.53:9.06                                                                        386(s), 400, 423(s),                                                           442(s), 527                             127  641.7                                                                               641 C.sub.38 H.sub.38 N.sub.4 O.sub.2.Co                                                    71.13:5.97:8.93                                                                        71.06:6.12:8.87                                                                        386(s), 400, 421(s),                                                           442(s), 527                             128  669.7                                                                               669 C.sub.40 H.sub.42 N.sub.4 O.sub.2.Co                                                    71.74:6.32:8.37                                                                        71.69:6.25:8.52                                                                        386(s), 400, 423(s),                                                           442(s), 527                             129  669.7                                                                               669 C.sub.40 H.sub.42 N.sub.4 O.sub.2.Co                                                    71.74:6.32:8.37                                                                        71.67:6.24:8.55                                                                        385(s), 400, 423(s),                                                           442(s), 527                             130  697.8                                                                               697 C.sub.42 H.sub.46 N.sub.4 O.sub.2.Co                                                    72.29:6.64:8.03                                                                        72.13:6.72:8.15                                                                        384(s), 400, 422(s),                                                           443(s), 526                             131  697.8                                                                               697 C.sub. 42 H.sub.46 N.sub.4 O.sub.2.Co                                                   72.29:6.64:8.03                                                                        72.41:6.47:8.10                                                                        384(s), 400, 422(s),                                                           443(s), 526                             132  697.8                                                                               697 C.sub.42 H.sub.46 N.sub.4 O.sub.2.Co                                                    72.29:6.64:8.03                                                                        72.36:6.74:7.88                                                                        385(s), 400, 422(s),                                                           442(s), 526                             133  697.8                                                                               697 C.sub.42 H.sub.46 N.sub.4 O.sub.2.Co                                                    72.29:6.64:8.03                                                                        72.44:6.52:7.97                                                                        386(s), 400, 423(s),                                                           442(s), 527                             134  725.8                                                                               725 C.sub.44 H.sub.50 N.sub.4 O.sub.2.Co                                                    72.81:6.94:7.72                                                                        72.72:7.13:7.64                                                                        384(s), 400, 422(s),                                                           443(s), 526                             135  753.9                                                                               753 C.sub.46 H.sub.54 N.sub.4 O.sub.2.Co                                                    73.29:7.22:7.43                                                                        73.22:7.13:7.59                                                                        384(s), 400, 423(s),                                                           442(s), 525                             136  782.0                                                                               781 C.sub.48 H.sub.58 N.sub.4 O.sub.2.Co                                                    73.73:7.48:7.17                                                                        73.88:7.38:7.13                                                                        384(s), 400, 423(s),                                                           443(s), 525                             137  810.0                                                                               809 C.sub.50 H.sub.62 N.sub.4 O.sub.2.Co                                                    74.14:7.72:6.92                                                                        74.08:7.86:6.85                                                                        384(s), 400, 423(s),                                                           443(s), 525                             138  669.7                                                                               669 C.sub.40 H.sub.42 N.sub.4 O.sub.2.Co                                                    71.74:6.32:8.37                                                                        71.70:6.19:8.55                                                                        386(s), 400, 423(s),                                                           442(s), 527                             139  725.8                                                                               725 C.sub. 44 H.sub.50 N.sub.4 O.sub.2.Co                                                   72.81:6.94:7.72                                                                        72.91:6.89:7.67                                                                        385(s), 400, 423(s),                                                           442(s), 527                             140  782.0                                                                               781 C.sub.48 H.sub.58 N.sub.4 O.sub.2.Co                                                    73.73:7.48:7.17                                                                        73.66:7.59:7.12                                                                        386(s), 400, 422(s),                                                           442(s), 526                             141  838.1                                                                               837 C.sub.52 H.sub.66 N.sub.4 O.sub.2.Co                                                    74.53:7.94:6.69                                                                        74.47:7.86:6.83                                                                        386(s), 400, 423(s),                                                           442(s), 526                             142  894.2                                                                               893 C.sub.56 H.sub.74 N.sub.4 O.sub.2.Co                                                    75.22:8.34:6.27                                                                        75.09:8.42:6.35                                                                        385(s), 400, 422(s),                                                           442(s), 525                             143  950.3                                                                               949 C.sub.60 H.sub.82 N.sub.4 O.sub.2.Co                                                    75.84:8.70:5.90                                                                        75.99:8.62:5.78                                                                        384(s), 400, 422(s),                                                           442(s), 526                             144  1006.4                                                                              1005                                                                               C.sub.64 H.sub.90 N.sub.4 O.sub.2.Co                                                    76.38:9.01:5.57                                                                        76.51:8.87:5.60                                                                        384(s), 400, 422(s),                                                           442(s), 526                             145  697.8                                                                               697 C.sub.42 H.sub.46 N.sub.4 O.sub.2.Co                                                    72.29:6.64:8.03                                                                        72.36:6.72:7.87                                                                        386(s), 400, 421(s),                                                           443(s), 527                             146  782.0                                                                               781 C.sub.48 H.sub.58 N.sub.4 O.sub.2.Co                                                    73.73:7.48:7.17                                                                        73.92:7.37:7.10                                                                        385(s), 400, 422(s),                                                           443(s), 526                             147  860.1                                                                               859 C.sub.54 H.sub.64 N.sub. 4 O.sub.2.Co                                                   75.41:7.50:6.51                                                                        75.38:7.46:6.49                                                                        385(s), 400, 422(s),                                                           442(s), 526                             148  950.3                                                                               949 C.sub.60 H.sub.82 N.sub.4 O.sub.2.Co                                                    75.84:8.70:5.90                                                                        75.77:8.87:5.79                                                                        385(s), 400, 423(s),                                                           443(s), 526                             149  1034.4                                                                              1033                                                                               C.sub.66 H.sub.94 N.sub.4 O.sub.2.Co                                                    76.63:9.16:5.42                                                                        76.81:9.07:5.35                                                                        384(s), 400, 422(s),                                                           442(s), 525                             150  1118.6                                                                              1117                                                                               C.sub.72 H.sub.106 N.sub.4 O.sub.2.Co                                                   77.31:9.55:5.01                                                                        77.45:9.61:4.84                                                                        384(s), 400, 423(s),                                                           443(s), 526                             151  1202.8                                                                              1201                                                                               C.sub.78 H.sub.118 N.sub.4 O.sub.2.Co                                                   77.89:9.89:4.66                                                                        77.81:10.02:4.59                                                                       384(s), 400, 422(s),                                                           443(s), 526                             152  525.5                                                                               525 C.sub.32 H.sub.26 N.sub.4.Co                                                            73.14:4.99:10.66                                                                       73.28:4.95:10.58                                                                       379(s), 389, 418,                                                              430(s), 522                             153  645.6                                                                               645 C.sub.36 H.sub.34 N.sub.4 O.sub.4.Co                                                    66.97:5.31:8.68                                                                        67.07:5.27:8.63                                                                        383, 428, 454,                                                                 527                                     154  673.7                                                                               673 C.sub.38 H.sub.38 N.sub.4 O.sub.4.Co                                                    67.75:5.69:8.32                                                                        67.68:5.82:8.19                                                                        383, 428, 454,                                                                 527                                     155  701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub. 4.Co                                                   68.46:6.03:7.98                                                                        68.41:5.98:8.13                                                                        383, 429, 456,                                                                 528                                     156  701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.46:6.03:7.98                                                                        68.33:6.10:8.04                                                                        383, 429, 455                                                                  527                                     157  729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.18:6.19:7.73                                                                        384, 428, 454,                                                                 526                                     158  729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.20:6.41:7.56                                                                        383, 428, 455,                                                                 527                                     159  729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.28:6.28:7.59                                                                        383, 428, 455,                                                                 527                                     160  729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        69.05:6.52:7.60                                                                        383, 429, 454,                                                                 527                                     161  757.8                                                                               757 C.sub.44 H.sub.50 N.sub.4 O.sub.4.Co                                                    69.74:6.65:7.39                                                                        69.67:6.62:7.53                                                                        383, 429, 456,                                                                 527                                     162  785.9                                                                               785 C.sub.46 H.sub.54 N.sub.4 O.sub.4.Co                                                    70.30:6.93:7.13                                                                        70.17:7.02:7.18                                                                        383, 428, 454,                                                                 526                                     163  813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.92:7.03:6.93                                                                        383, 428, 454,                                                                 526                                     164  842.0                                                                               841 C.sub.50 H.sub.62 N.sub.4 O.sub.4.Co                                                    71.32:7.42:6.65                                                                        71.39:7.53:6.47                                                                        383, 428, 455,                                                                 527                                     165  701.7                                                                               701 C.sub.40 H.sub.42 N.sub.4 O.sub.4.Co                                                    68.46:6.03:7.98                                                                        68.51:6.05:8.01                                                                        383, 428, 454,                                                                 527                                     166  757.8                                                                               757 C.sub.44 H.sub.50 N.sub.4 O.sub.4.Co                                                    69.74:6.65:7.39                                                                        69.70:6.74:7.33                                                                        384, 428, 456,                                                                 528                                     167  757.8                                                                               757 C.sub.44 H.sub.50 N.sub.4 O.sub.4.Co                                                    69.74:6.65:7.39                                                                        69.58:6.72:7.30                                                                        384, 428, 456,                                                                 528                                     168  813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.68:7.23:6.94                                                                        383, 429, 455,                                                                 527                                     169  813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.78:7.13:6.82                                                                        384, 429, 456,                                                                 528                                     170  813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.91:7.15:6.80                                                                        384, 428, 456,                                                                 527                                     171  813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.95:7.07:6.92                                                                        383, 428, 455,                                                                 527                                     172  870.1                                                                               869 C.sub.52 H.sub.66 N.sub.4 O.sub.4.Co                                                    71.79:7.65:6.44                                                                        71.85:7.72:6.29                                                                        384, 429, 455,                                                                 526                                     173  926.2                                                                               925 C.sub.56 H.sub.74 N.sub.4 O.sub.4.Co                                                    72.62:8.05:6.05                                                                        72.84:7.98:5.97                                                                        383, 428, 455,                                                                 527                                     174  982.3                                                                               981 C.sub.60 H.sub.82 N.sub.4 O.sub.4.Co                                                    73.37:8.41:5.70                                                                        73.23:8.60:5.61                                                                        383, 428, 455,                                                                 527                                     175  1038.4                                                                              1037                                                                               C.sub.64 H.sub.90 N.sub.4 O.sub.4.Co                                                    74.03:8.74:5.40                                                                        73.98:8.67:5.57                                                                        383, 428, 455,                                                                 527                                     176  729.8                                                                               729 C.sub.42 H.sub.46 N.sub.4 O.sub.4.Co                                                    69.12:6.35:7.68                                                                        68.97:6.42:7.74                                                                        384, 428, 454,                                                                 526                                     177  813.9                                                                               813 C.sub.48 H.sub.58 N.sub.4 O.sub.4.Co                                                    70.83:7.18:6.88                                                                        70.91:7.24:6.73                                                                        384, 428, 454,                                                                 527                                     178  898.1                                                                               897 C.sub.54 H.sub.70 N.sub.4 O.sub.4.Co                                                    72.22:7.86:6.24                                                                        72.37:7.78:6.17                                                                        383, 429, 455,                                                                 527                                     179  982.3                                                                               981 C.sub.60 H.sub.82 N.sub.4 O.sub.4.Co                                                    73.37:8.41:5.70                                                                        73.28:8.57:5.62                                                                        383, 428, 454,                                                                 526                                     180  1066.4                                                                              1065                                                                               C.sub.66 H.sub.94 N.sub. 4 O.sub.4.Co                                                   74.33:8.88:5.25                                                                        74.28:8.79:5.44                                                                        383, 428, 454,                                                                 526                                     181  1150.6                                                                              1149                                                                               C.sub.72 H.sub.106 N.sub.4 O.sub.4.Co                                                   75.16:9.29:4.87                                                                        75.03:9.36:4.92                                                                        383, 427, 454,                                                                 526                                     182  1234.8                                                                              1233                                                                               C.sub.78 H.sub.118 N.sub.4 O.sub.4.Co                                                   75.87:9.63:4.54                                                                        75.94:9.51:4.60                                                                        383, 428, 455,                                                                 526                                     183  553.6                                                                               553 C.sub.34 H.sub.30 N.sub.4.Co                                                            73.76:5.46:10.12                                                                       73.81:5.53:9.98                                                                        380(s), 393, 428(s),                                                           522                                     184  722.0                                                                               721 C.sub.46 H.sub.54 N.sub.4.Co                                                            76.53:7.54:7.76                                                                        76.50:7.49:7.72                                                                        380(s), 393, 428(s),                                                           522                                     185  609.7                                                                               609 C.sub.38 H.sub.38 N.sub.4.Co                                                            74.86:6.28:9.19                                                                        74.81:6.33:9.21                                                                        384, 398, 422,                                                                 439(s), 525                             186  637.7                                                                               637 C.sub.40 H.sub.42 N.sub.4.Co                                                            75.34:6.64:8.79                                                                        75.36:6.64:8.75                                                                        385, 398, 422,                                                                 438(s), 525                             187  637.7                                                                               637 C.sub.40 H.sub.42 N.sub.4.Co                                                            75.34:6.64:8.79                                                                        75.40:6.61:8.82                                                                        384, 397, 421,                                                                 438(s), 525                             188  665.8                                                                               665 C.sub.42 H.sub.46 N.sub.4.Co                                                            75.77:6.96:8.42                                                                        75.69:6.99:8.43                                                                        385, 397, 421,                                                                 438(s), 524                             189  665.8                                                                               665 C.sub.42 H.sub.46 N.sub.4.Co                                                            75.77:6.96:8.42                                                                        75.78:6.92:8.43                                                                        385, 397, 421,                                                                 438(s), 525                             190  665.8                                                                               665 C.sub.42 H.sub.46 N.sub.4.Co                                                            75.77:6.96:8.42                                                                        75.82:6.91:8.41                                                                        385, 397, 421,                                                                 438(s), 525                             191  665.8                                                                               665 C.sub.42 H.sub.46 N.sub.4.Co                                                            75.77:6.96:8.42                                                                        75.83:6.93:8.45                                                                        384, 398, 422,                                                                 439(s), 525                             192  693.8                                                                               693 C.sub.44 H.sub.50 N.sub.4.Co                                                            76.17:7.26:8.08                                                                        76.24:7.19:8.10                                                                        385, 397, 421,                                                                 438(s), 525                             193  721.9                                                                               721 C.sub.46 H.sub.54 N.sub.4.Co                                                            76.54:7.54:7.76                                                                        76.48:7.57:7.81                                                                        385, 397, 421,                                                                 438(s), 525                             194  750.0                                                                               749 C.sub.48 H.sub.58 N.sub.4.Co                                                            76.88:7.80:7.47                                                                        76.94:7.72:7.48                                                                        385, 397, 421,                                                                 438(s), 525                             195  778.0                                                                               777 C.sub.50 H.sub.62 N.sub.4.Co                                                            77.19:8.03:7.20                                                                        77.27:7.93:7.26                                                                        386, 397, 421,                                                                 438(s), 525                             196  637.7                                                                               637 C.sub.40 H.sub.42 N.sub.4.Co                                                            75.34:6.64:8.79                                                                        75.41:6.58:8.83                                                                        384, 398, 422,                                                                 439(s), 524                             197  693.8                                                                               693 C.sub.44 H.sub.50 N.sub.4.Co                                                            76.17:7.26:8.08                                                                        76.07:7.33:8.14                                                                        385, 398, 422,                                                                 439(s), 525                             198  750.0                                                                               749 C.sub.48 H.sub.58 N.sub.4.Co                                                            76.88:7.80:7.47                                                                        76.92:7.71:7.50                                                                        384, 397, 422,                                                                 439(s), 525                             199  806.1                                                                               805 C.sub.52 H.sub.66 N.sub.4.Co                                                            77.48:8.25:6.95                                                                        77.39:8.15:7.04                                                                        385, 398, 421,                                                                 439(s), 524                             200  862.2                                                                               861 C.sub.56 H.sub.74 N.sub.4.Co                                                            78.01:8.65:6.50                                                                        77.93:8.63:6.58                                                                        385, 398, 421,                                                                 439(s), 525                             201  918.3                                                                               917 C.sub.60 H.sub.82 N.sub.4.Co                                                            78.48:9.00:6.10                                                                        78.60:8.92:6.05                                                                        385, 397, 421,                                                                 439(s), 525                             202  974.4                                                                               973 C.sub.64 H.sub.90 N.sub.4.Co                                                            78.89:9.31:5.75                                                                        78.93:9.30:5.72                                                                        386, 397, 421,                                                                 439(s), 525                             203  665.8                                                                               665 C.sub.42 H.sub.46 N.sub.4.Co                                                            75.77:6.96:8.42                                                                        75.85:6.92:8.38                                                                        385, 397, 421,                                                                 438(s), 524                             204  750.0                                                                               749 C.sub.48 H.sub.58 N.sub.4.Co                                                            76.88:7.80:7.47                                                                        76.95:7.74:7.44                                                                        385, 397, 421,                                                                 438(s), 525                             205  834.1                                                                               833 C.sub.54 H.sub.70 N.sub.4.Co                                                            77.76:8.46:6.72                                                                        77.64:8.53:6.80                                                                        385, 397, 421,                                                                 439(s), 525                             206  918.3                                                                               917 C.sub.60 H.sub.82 N.sub.4.Co                                                            78.48:9.00:6.10                                                                        78.53:8.94:6.07                                                                        385, 397, 421,                                                                 439(s), 525                             207  1002.4                                                                              1001                                                                               C.sub.66 H.sub.94 N.sub.4.Co                                                            79.08:9.45:5.59                                                                        79.03:9.51:5.57                                                                        385, 397, 421,                                                                 439(s), 525                             208  1086.6                                                                              1085                                                                               C.sub.72 H.sub.106 N.sub.4.Co                                                           79.59:9.83:5.16                                                                        79.66:9.80:5.11                                                                        385, 397, 421,                                                                 439(s), 525                             209  1170.8                                                                              1169                                                                               C.sub.78 H.sub.118 N.sub.4.Co                                                           80.02:10.16:4.79                                                                       79.96:10.20:4.83                                                                       386, 397, 421,                                                                 438(s), 525                             __________________________________________________________________________      *.sup.(1) : (s) means a shoulder of a                                          *.sup.(2) : ˜ means a center wave length of a plateau peak.        

EXAMPLE 210

The oxygen reduction catalyst activities of Co-TAA as obtained in Examples 1, 3, 8, 19, 93, 96, 126, 140, 154, 168, 188 and 198 were measured. The measurement was carried out in accordance with the cyclic voltammetry method by using a potentiostat.

In 1 l of chloroform of 1 l of N,N-dimethylformamide was dissolved 800 mg of Co-TAA, and in the solution was dipped a Glassy Carbon (trade name; product of Tokai Denkyoku Seizo K.K.) whose surface was mirror-plane finished for 30 minutes. The Glassy Carbon was taken out from the solution and left to stand to dryness. The treated glassy carbon was employed as a cathode electrode. A platinum coil was employed as an anode electrode and a calomel electrode was employed as a reference electrode. An electrolytic solution was 1N sulfuric acid and the measurement temperature was 25° C.

The measurement was carried out by introducing a high-purity oxygen gas into the electrolytic solution and recording the electric current generated by varying the voltage from +800 mV to -600 mV at a velocity of 25 mV/sec.

The catalyst activity was evaluated by the generated electric current value at +375 mV. The measurement was repeated 10 times and the catalyst life was evaluated by the tenth measurement result, that is, the tenth catalyst activity. The measurement results are shown in Table 2.

                  TABLE 2                                                          ______________________________________                                         Catalyst                                                                       obtained in  Catalyst Activity                                                                           Catalyst Life                                        Example No.  (μA/cm.sup.2)                                                                            (μA/cm.sup.2)                                     ______________________________________                                          1           125          125                                                   3           165          165                                                   8           138          138                                                   19          167          167                                                   93          158          158                                                   96          157          157                                                  126          145          145                                                  140          152          152                                                  154          150          149                                                  168          144          144                                                  188          144          144                                                  198          147          147                                                  ______________________________________                                    

COMPARATIVE EXAMPLE

The catalyst activity and the catalyst life of Co-TAA having the formula (VII) were measured by the same methods as those of this invention. The Co-TAA has a catalyst activity of 145 μA/cm² and a catalyst life of 30 μA/cm².

EXAMPLE 211 ##STR63##

In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a β-ethoxy-α-arylacrolein and 0.02 mol of an o-phenylenediamine derivative as set forth in Table 3. The solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 3. All the compounds were confirmed as tetraazaannulene derivatives.

                  TABLE 3                                                          ______________________________________                                          No.Experimental                                                                         ##STR64##                                                                                   ##STR65##      (%)Yield                                 ______________________________________                                         1        H            H         H      34                                      2        O.sub.2 N    H         H      26                                      3        CH.sub.3 O   H         H      27                                      4        CH.sub.3     H         H      31                                      5        NC           H         H      30                                      6        HOOC         H         H      30                                      7        Cl           H         H      27                                      8        Br           H         H      28                                      9        H            CH.sub.3  CH.sub.3                                                                              18                                      10       H            CH.sub.3  CH.sub.3                                                                              29                                      11       H            Cl        H      16                                      12       H            Cl        Cl     33                                      13       H            CH.sub.3 O                                                                               H      3                                       14       H            COOH      CH.sub.3                                                                              3                                       15       H            O.sub.2 N H      5                                       ______________________________________                                          ##STR66##

In 10 ml of N,N-dimethylformamide were dissolved 5 millimol of each of the tetraazaannulene derivatives obtained in Step 1 and 5 millimol of cobalt (II) acetate tetrahydrate, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound was filtered, washed with methanol and dried. All the compounds were obtained at a yield of 90˜95%, and identified as Co-TAA having the formula (II') by elementary analysis, the mass spectra and visible spectra thereof.

EXAMPLE 212 ##STR67##

In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a β-alkoxy-α-phenylacrolein as set forth in Table 4 and 2.16 g (0.02 mol) of o-phenylenediamine, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 4. All the compounds were confirmed as the tetraazaannulene derivative.

                  TABLE 4                                                          ______________________________________                                          No.mentalExperi-                                                                      ##STR68##       (%)Yield                                                                                (nm)[in DMF]Visible Spectrum                  ______________________________________                                         1      CH.sub.3        33       390, 427, 446                                  2      CH.sub.3 CH.sub.2                                                                              34       390, 427, 446                                  3      CH.sub.3 CH.sub.2 CH.sub.2                                                                     32       390, 427, 446                                  4      CH.sub.3 (CH.sub.2).sub.3                                                                      33       390, 427, 446                                  5      CH.sub.3 (CH.sub.2).sub.5                                                                      34       390, 427, 446                                    6                                                                                    ##STR69##      30       390, 427, 446                                    7                                                                                    ##STR70##      32       390, 427, 446                                  ______________________________________                                    

EXAMPLE 213 ##STR71##

In 20 ml of N,N-dimethylformamide were dissolved 5 millimol of an o-phenylenediamine derivative as set forth in Table 5 and 623 mg (2.5 millimol) of cobalt (II) acetate tetrahydrate, and the solution was heated at 120° C. The solution was added with 5 millimol of a β-ethoxy-α-arylacrolein as set forth in Table 5 and refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound at a yield as shown in Table 5. All the compounds were confirmed as Co-TAA.

                  TABLE 5                                                          ______________________________________                                          No.Experimental                                                                         ##STR72##                                                                                   ##STR73##      (%)Yield                                 ______________________________________                                         1        H            H         H      52                                      2        O.sub.2 N    H         H      38                                      3        CH.sub.3 O   H         H      37                                      4        CH.sub.3     H         H      37                                      5        NC           H         H      40                                      6        H            CH.sub.3  H      31                                      7        H            CH.sub.3  CH.sub.3                                                                              35                                      8        H            Cl        H      22                                      9        H            Cl        Cl     40                                      10       H            CH.sub.3 O                                                                               H      8                                       11       CH.sub. 3 O  Cl        H      47                                      12       O.sub.2 N    CH.sub.3  H      36                                      13       CH.sub.3     CH.sub.3  CH.sub.3                                                                              66                                      ______________________________________                                    

EXAMPLE 214

The same procedures as described in Experimental No. 1 of Example 213 were repeated except that a β-ethoxy-α-arylacrolein as set forth in Table 6 was employed instead of the β-ethoxy-α-phenylacrolein. All the compounds obtained were confirmed as Co-TAA. The yield of Co-TAA is shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                   ##STR74##                                                            Experimental            Position Yield                                         No.        R.sub.4      of R.sub.4                                                                              (%)                                           ______________________________________                                         1          CH.sub.3     ortho    31                                            2          CH.sub.3 O   ortho    25                                            3          CH.sub.3     meta     43                                            4          CH.sub.3 O   meta     37                                            5          Cl           ortho    28                                            6          Cl           meta     34                                            ______________________________________                                    

EXAMPLE 215 ##STR75##

In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (540 mg) of o-phenylenediamine and 2.5 millimol (623 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated to 120° C. Then, the solution was added with 5 millimol of a β-alkoxy-α-phenylacrolein as set forth in Table 7, and refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound at a yield as shown in Table 7. All the compounds were confirmed as Co-TAA.

                  TABLE 7                                                          ______________________________________                                          mentalExperi-                                                                        ##STR76##        Yield   [in DMF]Visible Spectrum                       No.   R.sub.7          (%)     (nm)                                            ______________________________________                                         1     CH.sub.3         52      377(s)*, 388, 425(s),                                                          522                                             2     CH.sub.3 CH.sub.2                                                                               54      377(s), 388, 425(s),                                                           522                                             3     CH.sub.3 CH.sub.2 CH.sub.2                                                                      50      377(s), 388, 425(s),                                                           522                                               4   CH.sub.3 (CH.sub.2).sub.3                                                                       51      377(s), 388, 425(s),                                                           522                                             5     CH.sub.3 (CH.sub.2).sub.5                                                                       50      377(s), 388, 425(s),                                                           522                                               6                                                                                   ##STR77##       49      377(s), 388, 425(s), 522                          7                                                                                   ##STR78##       53      377(s), 388, 425(s), 522                        ______________________________________                                    

EXAMPLE 216 ##STR79##

In 30 ml of N,N-dimethylformamide were dissolved 0.02 mol of a β-dimethylamino-α-arylacrolein and 0.02 mol of an o-phenylenediamine derivative as set forth in Table 8, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to separate a compound. The compound obtained was separated by filtration, washed with methanol and dried under reduced pressure. The yield is shown in Table 8. All the compounds were confirmed as tetraazaannulene derivatives.

                  TABLE 8                                                          ______________________________________                                          Experimental                                                                            ##STR80##                                                                                   ##STR81##      Yield                                    No.      R.sub.4      R.sub.5  R.sub.6 (%)                                     ______________________________________                                         1        H            H        H       54                                      2        O.sub.2 N    H        H       39                                      3        CH.sub.3 O   H        H       39                                      4        CH.sub.3     H        H       49                                      5        H            CH.sub.3 H       25                                      6        H            CH.sub.3 CH.sub.3                                                                               52                                      7        H            CH.sub.3 O                                                                              H       5                                       8        CH.sub.3     CH.sub.3 O                                                                              H       4                                       9        CH.sub.3     CH.sub.3 O                                                                              CH.sub.3 O                                                                             7                                       10       O.sub.2 N    CH.sub.3 CH.sub.3                                                                               59                                      11       CH.sub.3 O   CH.sub.3 O                                                                              H       8                                       12                                                                                       ##STR82##   CH.sub.3 O                                                                              H       6                                       13       CH.sub.3 O   CH.sub.3 O                                                                              CH.sub.3 O                                                                             10                                      ______________________________________                                          ##STR83##

In 10 ml of N,N-dimethylformamide were dissolved 5 millimol of each of the tetraazaannulene derivatives obtained and 5 ml of cobalt (II) acetate tetrahydrate, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. All the compounds were obtained at a yield of 90-95%, and confirmed as Co-TAA.

EXAMPLE 217 ##STR84##

In 30 ml of N,N-dimethylformamide were dissolved 0.02 mol of a β-dialkylamino-α-phenylacrolein as set forth in Table 9 and 2.16 g (0.02 mol) of o-phenylenediamine, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried under reduced pressure. The yield is shown in Table 9. All the compounds were confirmed as the tetraazaannulene derivative.

                  TABLE 9                                                          ______________________________________                                          perimentalEx-                                                                          ##STR85##         Yield   [in DMF]SpectrumVisible                     No.     R.sub.8    R.sub.9    (%)   (nm)                                       ______________________________________                                         1       CH.sub.3   CH.sub.3   54    390, 427, 446                              2       CH.sub.3 CH.sub.2                                                                         CH.sub.3 CH.sub.2                                                                         51    390, 427, 446                              3       CH.sub.3   CH.sub.3 CH.sub.2                                                                         53    390, 427, 446                              4       CH.sub.3   CH.sub.3 (CH.sub.2).sub.3                                                                 50    390, 427, 446                              5       CH.sub.3 (CH.sub.2).sub.3                                                                 CH.sub.3 (CH.sub.2).sub.3                                                                 52    390, 427, 446                              ______________________________________                                    

In N,N-dimethylformamide were dissolved the tetraazaannulene obtained and the equimolar amount of cobalt (II) acetate tetrahydrate, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. All the compounds were obtained in a yield of 90-95%, and confirmed as Co-TAA.

EXAMPLE 218 ##STR86##

In 20 ml of N,N-dimethylformamide were dissolved 5 millimol of an o-phenylenediamine derivative as set forth in Table 10 and 623 mg (2.5 millimol) of cobalt (II) acetate tetrahydrate, and the solution was heated at 120° C. for 30 minutes. The solution was added with 5 millimol of a β-dimethylamino-α-arylacrolein as set forth in Table 10, and refluxed under heating for 5 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound. The yield is shown in Table 10. All the compounds were confirmed as Co-TAA.

                  TABLE 10                                                         ______________________________________                                          perimentalEx-                                                                          ##STR87##                                                                                    ##STR88##      Yield                                    No.     R.sub.4       R.sub.5   R.sub.6                                                                               (%)                                     ______________________________________                                          1      CH.sub.3      H         H      58                                       2      O.sub.2 N     H         H      63                                       3      CH.sub.3 O    H         H      60                                       4      Cl            H         H      67                                       5      H             CH.sub.3  H      45                                       6      H             CH.sub.3  CH.sub.3                                                                              72                                       7      H             Cl        Cl     54                                       8      CH.sub.3      CH.sub.3 O                                                                               H       9                                       9      CH.sub.3      CH.sub.3 O                                                                               CH.sub.3 O                                                                            14                                      10      NC            Cl        Cl     67                                        11                                                                                    ##STR89##    CH.sub.3 O                                                                               H      10                                        12    O.sub.2 N     CH.sub.3  CH.sub.3                                                                              73                                      13      CH.sub.3 O    CH.sub.3 O                                                                               H      15                                      14      CH.sub.3 O    CH.sub.3 O                                                                               CH.sub.3 O                                                                            17                                      ______________________________________                                    

EXAMPLE 219 ##STR90##

In 20 ml of N,N-dimethylformamide were dissolved 5 millimol (540 mg) of o-phenylenediamine and 2.5 millimol (623 mg) of cobalt (II) acetate tetrahydrate, and the solution was heated at 120° C. for 30 minutes. The solution was added with 5 millimol of a β-dialkylamino-α-phenylacrolein as set forth in Table 11, and refluxed under heating for 3 hours. The reaction solution was cooled, filtered, washed with methanol and dried to give a compound at a yield as shown in Table 11. All the compound obtained were confirmed as Co-TAA.

                  TABLE 11                                                         ______________________________________                                          Experimental                                                                            ##STR91##         Yield   [in DMF]SpectrumVisible                    No.      R.sub.8    R.sub.9    (%)   (nm)                                      ______________________________________                                         1        CH.sub.3   CH.sub.3   72    377(s)*, 388                                                                   425(s), 522                               2        CH.sub.3 CH.sub.2                                                                         CH.sub.3 CH.sub.2                                                                         63    377(s), 388                                                                    425(s), 522                               3        CH.sub.3   CH.sub.3 CH.sub.2                                                                         68    377(s), 388                                                                    425(s), 522                               4        CH.sub.3   CH.sub.3 (CH.sub.2).sub.3                                                                 64    377(s), 388                                                                    425(s), 522                               5        CH.sub.3 (CH.sub.2).sub.3                                                                 CH.sub.3 (CH.sub.2).sub.3                                                                 65    377(s), 388                                                                    425(s), 522                               ______________________________________                                    

EXAMPLE 220 ##STR92##

In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a β-ethoxy-α-arylacrolein and 0.02 mol of an o-phenylenediamine derivative as set forth in Table 12, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 12. All the compounds were confirmed as tetraazaannulene derivatives.

                  TABLE 12                                                         ______________________________________                                          mentalExperi-                                                                          ##STR93##                                                                                    ##STR94##      Yield                                    No.     R.sub.4  of R.sub.4                                                                              R.sub.5                                                                               R.sub.6 (%)                                   ______________________________________                                          1      CH.sub.3 ortho    H      H       13                                     2      CH.sub.3 meta     H      H       18                                     3      CH.sub.3 O                                                                              ortho    H      H       15                                     4      CH.sub.3 O                                                                              meta     H      H       17                                     5      Cl       ortho    H      H       14                                     6      Cl       meta     H      H       19                                     7      O.sub.2 N                                                                               ortho    H      H       17                                     8      O.sub.2 N                                                                               meta     H      H       21                                     9      CH.sub.3 O                                                                              ortho    Cl     Cl      16                                    10      CH.sub.3 O                                                                              meta     Cl     Cl      20                                    ______________________________________                                    

EXAMPLE 221 ##STR95##

In 25 ml of N,N-dimethylformamide were dissolved 0.02 mol of a β-dimethylamino-α-arylacrolein and 0.02 mol of an o-phenylenediamine derivative as set forth in Table 13, and the solution was refluxed under heating for 5 hours. The reaction solution was cooled to 25° C. to give a compound. The compound obtained was separated by filtration, washed with methanol and dried. The yield is shown in Table 13. All the compounds were confirmed as tetraazaannulele derivatives.

                  TABLE 13                                                         ______________________________________                                          mentalExperi-                                                                        ##STR96##                                                                                      ##STR97##      Yield                                    No.   R.sub.4   of R.sub.4                                                                               R.sub.5                                                                               R.sub.6 (%)                                   ______________________________________                                          1    CH.sub.3  ortho     H      H       15                                     2    CH.sub.3  meta      H      H       22                                     3    CH.sub.3 O                                                                               ortho     H      H       20                                     4    CH.sub.3 O                                                                               meta      H      H       23                                     5    Cl        ortho     H      H       21                                     6    Cl        meta      H      H       25                                     7    O.sub.2 N ortho     H      H       24                                     8    O.sub.2 N meta      H      H       27                                     9    CH.sub.3 O                                                                               ortho     Cl     Cl      23                                    10    CH.sub.3 O                                                                               meta      Cl     Cl      28                                    ______________________________________                                     

What is claimed is:
 1. A tetraazaannulene cobalt complex compound having the general formula (I); ##STR98## wherein R₁, R₂ and R₃ each independently is a hydrogen atom, a C₁₋₈ alkoxy group or a C₁₋₈ alkyl group but in case of one of R₁, R₂ and R₃ being a hydrogen atom the other two groups are not hydrogen atoms at the same time, and when R₁ is a methyl group R₂ and R₃ are not hydrogen atoms at the same time.
 2. The compound of claim 1, wherein R₁ is a C₁₋₈ alkoxy group.
 3. The compound of claim 2, wherein R₂ and R₃ each independently is a C₁₋₈ alkoxy group.
 4. The compound of claim 2, wherein one of R₂ and R₃ is a C₁₋₈ alkoxy group and the other group is a hydrogen atom.
 5. The compound of claim 2, wherein R₂ and R₃ each independently is a hydrogen atom or a C₁₋₈ alkyl group.
 6. The compound of claim 1, wherein R₁ is a C₁₋₈ alkyl group.
 7. The compound of claim 6, wherein R₂ and R₃ each independently is a C₁₋₈ alkoxy group.
 8. The compound of claim 6, wherein R₂ and R₃ each independently is a C₁₋₈ alkyl group or a hydrogen atom.
 9. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II); ##STR99## wherein R₄ is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ alkylcarboxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkylamido group, an amino group, a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group or a N,N-di C₁₋₆ alkylamino C₁₋₃ alkyl group;n is integer of 1 to 5; and R₅ and R₆ each independently is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ alkylcarboxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkylamido group, or a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group;which comprises reacting a β-alkoxy-α-arylacrolein of the general formula (III); ##STR100## wherein R₄ and n are the same as defined in the formula (II); and R₇ is a C₁₋₆ alkyl group;with an o-phenylenediamine derivative of the general formula (IV); ##STR101## wherein R₅ and R₆ are the same as defined in the formula (II); to prepare a tetraazaannulene derivative of the formula (V); ##STR102## wherein R₄, R₅, R₆ and n are the same as defined in the formula (II); and reacting the tetraazaannulene derivative of the formula (V) with a cobalt compound.
 10. The method of claim 9, wherein the reaction between the β-alkoxy-α-arylacrolein of the general formula (III) and the o-phenylenediamine derivative of the general formula (IV) is carried out at 50°-250° C.
 11. The method of claim 9, wherein the reaction between the tetraazaannulene derivative of the formula (V) and the cobalt compound is carried out at 50°-250° C.
 12. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II) as defined in claim 9 which comprises reacting a -alkoxy-arylacrolein of the general formula (III) as defined in claim 9 and an o-phenylenediamine derivative of the general formula (IV) as defined in claim 9 in the presence of a cobalt compound.
 13. The method of claim 12, wherein the reaction is carried out at 50°-250° C.
 14. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II) as defined in claim 9 which comprises reacting a β-dialkylamino-α-arylacrolein of the general formula (VI): ##STR103## wherein R₄ and n are the same as defined in the formula (II); andR₈ and R₉ each independently is a C₁₋₆ alkyl group; with an o-phenylenediamine derivative of the general formula (IV) as defined in claim 9 to prepare a tetraazaannulene derivative of the formula (V) as defined in claim 9, and reacting the tetraazaannulene derivative with a cobalt compound.
 15. The method of claim 14, wherein the reaction between the β-dialkylamino-α-arylacrolein of the general formula (VI) and the o-phenylenediamine derivative of the general formula (IV) is carried out at 50°-250° C.
 16. The method of claim 14, wherein the reaction between the tetraazaannulene derivative of the formula (V) and the cobalt compound is carried out at 50°-250° C.
 17. A method for preparing a tetraazaannulene cobalt complex compound having the general formula (II) as defined in claim 9 which comprises reacting a β-dialkylamino-α-arylacrolein of the general formula (VI) as defined in claim 9 with an o-phenylenediamine derivative of the general formula (IV) as defined in claim 9 in the presence of a cobalt compound.
 18. The method of claim 17, wherein the reaction is carried out at 50°-250° C.
 19. A method for preparing a tetraazaannulene derivative of the formula (V): ##STR104## wherein R₄ is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ alkylcarboxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkylamido group, an amino group, a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group or a N,N-di C₁₋₆ alkylamino C₁₋₃ alkyl group;n is integer of 1 to 5; and R₅ and R₆ each independently is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ alkylcarboxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkylamido group, or a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group;which comprises reacting a β-alkoxy-α-arylacrolein of the general formula (III): ##STR105## wherein R₄ and n are the same as defined in the formula (V); and R₇ is a C₁₋₆ alkyl group; with an o-phenylene-diamine derivative of the general formula (IV): ##STR106## wherein R₅ and R₆ are the same as defined in the formula (V).
 20. The method of claim 19, wherein the reaction is carried out at 50°-250° C.
 21. A method for preparing a tetraazaannulene derivative of the formula (V): ##STR107## wherein R₄ is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ alkylcarboxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkylamino group, an amino group, a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group or a N,N-di C₁₋₆ alkylamino C₁₋₃ alkyl group;n is integer of 1 to 5; and R₅ and R₆ each independently is a hydrogen atom, a C₁₋₈ alkoxy group, a C₁₋₈ alkyl group, a halogen atom, a nitro group, a cyano group, a C₁₋₈ alkylcarboxyl group, a hydroxyl group, a carboxyl group, a C₁₋₈ alkoxycarbonyl group, a carbamoyl group, a N,N-di C₁₋₆ alkylamino group, a C₁₋₈ alkylamido group, or a C₁₋₈ alkoxycarbonyl C₁₋₃ alkyl group; which comprises reacting a β-dialkylamino-α-arylacrolein of the general formula (VI): ##STR108## wherein R₄ and n are the same as defined in the formula (V); and R₈ and R₉ each independently is a C₁₋₆ alkyl group; with an o-phenylene-diamine derivative of the general formula (IV): ##STR109## wherein R₅ and R₆ are the same as defined in the formula (V).
 22. The method of claim 21, wherein the reaction is carried out at 50°-250° C. 